IL117864A - Benzamidoxime derivatives, their preparation and fungicidal compositions containing them - Google Patents

Abstract

Benzamidoximes of the formula wherein R1 is straight-chain or branched C1-C4 alkyl; a group represented by a general formula, R3CH2, wherein R3 is a group selected from a group consisting of C3-C8 cycloalkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkoxycarbonyl, cyano, amino, C1-C3 monoalkylamino, C1-C3 dialkylamino, acylamino and cyano; C2-C4 alkenyl or C2-C4 alkynyl, R2 is phenyl optionally having one or more substituents selected from a group consisting of halogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl and C1-C3 haloalkoxy; or a heterocycle group selected from pyrazolyl or thienyl which are optionally substituted by C1-C4 alkyl, X1 is C1-C4 haloalkyl, X2, X3, X4 and X5 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, nitro, amino or C1-C4 alkylcarbonylamino, and r1 and r2 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 alkylthio or amino, or r1 and r2 may form carbonyl together. 45 ז' באייר התשס" א - April 30, 2001

Description

1 17864/3 Benzamidoxime derivatives, their preparation and fungicidal compositions containing them Nippon Soda Co., Ltd.

C. 101746 D E S C R I P T I O N 1 BENZAMI DOX I E DERIVATIVES, METHOD FOR PREPARATION THEREOF AND FUNGICIDE FOR AGRICULTURAL AND HORTICULTURAL USE Technical Field: The present invention relates to novel benzamidox ime derivatives, methods for preparation thereof and fungicides for agricultural and horticultural uses.

Background Art: In farming of agricultural and horticultural crops in the past, various fungicides have been used for the control of plant diseases on the crops, however, many of them are not enough useful because of their insufficient effectiveness in plant disease control, the limitation in their use due to the appearance of resistant strain of plant disease pathogens to the fungicides, the development of phy totox i c i ty and contamination to the crops, and/or their strong toxicity to humans, domestic animals and wildlife. For this reason, there is sti ll intensive requirement to develop safe fungicides for agricultural and horticultural uses, which do not have the disadvantages as described above.

Some benzamidoxime derivatives, which are close to the compounds of the present invention, and their use as fungicides have been disclosed in Japanese Patent Laid-opened No. Hei 2-6453 Gazette. However, it is obvious that the biological activity of those benzamide oxime derivatives are not enough in the practical plant disease control.

Therefore, it is an object of the present invention to provide novel compounds which can be a fungicide for agricultural and horticultural use capable of advantageously manufacturing the compound in an industrial scale, controlling plant diseases steadily and using it safely.

Disclosure of the Invention: The present invention is directed to benzamidoxime derivatives wherein R1 is straight-chain or branched C - C 4 a 1 ky 1 ; a group represented 'by a general formula, R3CH2, wherein R 3 is a group selected from a group consisting of C3 - C8 cycloalkyl, d - C3 haloalkyl, Ct - C3 .alkoxy, Ci - C3 alkyl thio, Ci - C8 a 1 ky 1 s u 1 f i n 1 , Ci - C3 a Iky Is.u If ony 1, Ct - C3 a ikoxycar bo y 1, cyano, amino, Ci - C3 monoalkylamino, Ci - C3 dialky iamino, acylamino and cyano; C∑ - C4 alkenyl or C2 - C4 a Iky ay 1, R2 is phenyl optionally having one or more substituents selected from a group consisting of halogen, Ct ÷ C3 alky 1, Ci - C3 alkoxy, Ci - C3 haloalkyl and Ci - C3 haloalkoxy; or a heterocycle group selected from pyrazolyl or thienyl which are optionally substituted by Ci - C4 alkyl, . X1 is Ci - C4 haloalkyl, ' X'f, X3, X4 and Xs are each independently hydrogen, halogen, Ci - C alkyl, Ci - C4 haloalkyl, Ci - C4 alkoxy, Ci - C4 haloalkoxy, Ci - C4 alkylthio, Ct. - G alkylsulf iny.l,. Ci - C4 alkylsulf ony 1, nitro, amino or Ci - C4 alkylcarbonylamin , and r: and r3 are each independently hydrogen, halogen. Ci - C4 alkyl, C - C* haloalkyl, Ci - C4 alkoxy, Ci - C alkylthio or amino, or r_ and τζ may form carbonyl in together. 117864/2 For the examples' of the Ci - C4 haloalkyl represented by X1, straight chain or branched Ci - C4 haloalkyl, such as chloromethy 1, d ichloromethy 1, tr ichloromethyl. d i f.J ugrome thy 1. trif luoromethy 1, bromometh 1, dibromomethyl, chloroethy 1. fluoroethyl, dichloroethyl, d i f 1 uo roe thy 1, tr if luoroethyl, tetraf luoroethyl, pentaf luoroethy 1, chloropropyl, f luoropropyl, perf luoropro yl, chloroisopropyl, f 1 u o ro i sop r op y 1 , p e rf 1 uo ro i sop ropy 1 , chlorobutyl, f luorobutyl, perf luorobutyl, chloroisobutyl, f luoroisobutyl, perf luoroisobutyl, chloro-s-buty 1, f 1 uoro-s-bu ty 1, perf luoro-s-buty 1, chloro-t-butyl, f luoro-t-butyl and perf luoro-t-butyl, can be given.

For the examples of halogen atoms represented by X2, X3, X4 and Xs, f luorine, chlorine, bromine and iodine can be given, and for the examples of the Ci - C4 alkyl represented by X2. X3, X4 and X5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl can be given, and further for the examples of the Ci - C4 haloaikyl represented by X2, X3, X4 and X3, straight chain or branched C i - C haloaikyl, such as ch 1 or ome t hy 1. d ichloromethyl, trichloromethyl, d i f I u o r ome t hy 1 , trif 1 uo rome thy 1 , bromomethy 1, d i bromome thy 1, chloroethyl, fluoroethyl, d ichloroethy 1, d i f 1 uo r oe t hy 1 , t r i f 1 uo r o e t hy 1 , t e t r af 1 uo r oe t hy 1 , pentaf 1 uoroethy 1, ch 1 o rop r opy 1 , f 1 uo r op ropy 1 , p e r f 1 u o r op r op y 1 , chloroisopropyl, f 1 uo ro i sop ropy 1 , p e rf 1 uoro i sop ropy 1 , chlorobutyl, f l uorobuty l, e r f 1 u o r o b u t y 1 , chloro isobutyl. f 1 u o r o i s o b u t y 1 , perf luoroisobuty 1, ch loro-s-bu ty 1. fluoro-s-butyl, per f 1 uoro-s-bu ty 1, chloro-t-buty 1, f luoro-t-butyl and perf luoro'-t-buty 1, can be given, and still for the examples of the Ci - C4 alkoxy represented by X2, X3, X4 and X5, methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy and t-butyloxy can be given. In addition, for the examples of the Ci -C4 alkylthio represented by X2, X3, X4 and X5, methyl t h i o, ethylthio, propylthio, isopropyl thio, butylthio, isobutylthio and t-butyl thio can be given, and for the examples of the d - C4 haloalkoxy represented by X2, X3, X4 and X5, trif luoromethoxy, dif luoromethoxy, tr ichloromethoxy, trif luoroethoxy and tetraf luoroethoxy can be given.

Furthermore, for the examples of the groups represented .by rl and r2, which may be the same or different groups with each other, hydrogen, halogen atoms, such as fluorine, chlorine, bromine and iodine, Ci - C4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl, Ci - C4 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and t-butoxy, Ci - C4 alkylthio, such as methylthio, ethylthio, propylthio, ispropy 1 thio, butylthio and t-butylthio, Ci - C haloaikyl, such as t r i f 1 uo rome thy 1 , trichloromethyl, t r i b romome t hy 1 , t r i f 1 uo r oe t hy 1 , ch 1 o rome thy 1 , fluoromethyl and pentaf luoroethyl, and amino can be given. Moreover, r1 and r2 may in together form a carbonyl group.

(Manufacturing of the Compounds) The compounds of the present invention can be manufactured according to the following reaction formula; wherein Hal represents halogen, and R1. R2, X1, X2. X3, X4. X8. n and Γ2 are as described above.

The reaction described above is carried out by reacting the compound represented by the general formula [II] and the compound represented by the general formula [III] in an organic solvent for from 10 min. to several dozens of hours at a temperature range of from 0eC to the boiling point of the solvent used and in the presence of a base, if appropriate.

For the examples of the solvent usable in the reaction described above, aromatic hydrocarbons, such as benzene and toluene, ethers, such as THF and diethyl ether, halogenated hydrocarbons, such as chloroform and dichloro methane, amides, such as DMF, DMSO, acetonitrile and the mixture of the solvent exemplified above, can be given.

As the base usable in the reaction, pyridine, triethyl amine, DBU, sodium hydroxide, sodium carbonate, potassium carbonate or the like can be exempl ified.

After completed the reaction, the objective compounds can be obtained by taking an ordinary post-treatment procedure and allowing the products to the purification by using silica gel column chromatography or the else.

Whereas, the raw material compound of the present invent ion, represented by the general formula [II] can be synthesized according to the following reaction formula; wherein L is an el iminating group, such as paratoluenesu 1 f ony loxy, me thy 1 su I f ony 1 oxy and halogen atoms, and R\ X1, Xz, X3. X" and X5 are as described above.

The f irst step reaction in the reaction formula shown above is to obtain a benzamide oxime compound represented by the general formula [V], wherein a nitrile compound represented by the general formula [IV] and hydroxyl amine hydrochloride are allowed to a reaction for 10 min. to several dozens of hours in an inactive solvent and in the presence of a base at a temperature range of from 0 °C to the boiling point of the solvent used.

For the examples of the solvent usable in the reaction described above, alcohols, such as methanol, ethanol and propanol, ethers, such as THF and diethyl ether, amides, such as DMF, DMSO, water and the mixture of the solvent exemplified hereinabove, can be given.

Further, for the examples of the base usable in the reaction described above, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethyl amine, pyridine and the like can be given.

The second step reaction in the reaction formula shown above is to obtain the raw material compound represented by the general formula [II], wherein the compound represented by the general formula [V] and a compound represented by a general formula, Rl-L, are al lowed to a reaction for 10 min. to several dozens of hours in a solvent and in the presence of a base at a temperature range of. from -15 °C to the boiling point of the solvent used.

For the examples of the base usable in the second step reaction, metal alkoxide, such as sodium methoxide and sodium ethoxide, inorganic bases, such as sodium hydride, sodium hydroxide, potassium hydroxide and potassium carbonate, and organic bases, such as triethyl amine and pyridine, can be given.

Furthermore, if appropriate, catalysts may be used in the second step reaction, though it depends on the type of the solvent and the base to be used. For the examples of the catalysts usable in the reaction, crown ethers, such as 18-crown-6 and dicyclohexyl-18-crown-6, tetrabutyl ammonium bromide and other chlorides, quaternary ammonium salts, such as me t hy 11 r i o c t y 1 ammonium chloride and benzy 11 r i e thy 1 ammonium chloride, and phosphonium salts, such as tetraphenyl phosphonium bromide and hexadecyl tr ibuty 1 phosphonium iodide, can be given.

The chemical structures of the compounds of the present invention were determined by us ing NMR, IR, MS and the other analyt ical apparatuses.

Best Mode for Carrying Out the Invention: Now, the present invention is further described in detail with referring to the examples described hereinbelow.

Example 1 | Preparation of N' -cyclopropylmethyloxy-N-(4-methoxyphenyl)acetyl-2-f 1 uoro-6- tr i f 1 uorome thy lbenzami d ine (Compound No. 56) In 200ml of benzene was dissolved 20. Og of N' -cyclopropylmethyloxy-2-f 1 uoro-6- 1 r i f luoromethylbenzamidine, and to the solution was added 16. Og of 4-methoxypheny lacety lchlor ide. The solution was heated under refluxing for 10 hours. After cooling, ethyl acetate was added to the solution, followed by washing with water and drying over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure and the res idue was subjected to s i l ica ge l co lumn chromatography to obtain 23.6g of the objective compound. m. p. 75-76°C Example 2 Preparat ion N' -cyclopropylmethyloxy-N -(4-methoxyphenyl)acetyl-2-trif 1 uoromethy 1 benzamid ine (Compound No. 12) - - In 80ml of benzene was dissolved 10. g of N' -cy c 1 op ropy lme t hy 1 oxy-2-f litoro-6- 1 r i f luorometh lbenzamidine, and to the solution was added 8.9g of 4-me thoxypheny lace ty 1 ch lor i de. The solut ion was heated under ref luxing for 3 hours. After cooling, ethyl acetate was added to the solution, fol lowed by washing with water and drying over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure and the residue obtained in crystal was washed with a mixed solvent hexane and ether to thereby obtain 13.7g of crude crystal. The crystal was then re-crystallized in hexane, thereby affording 11.5g of the objective compound, m. p. 88-90 °C Now, the examples for preparing the raw material compounds described above to be used for the preparing of the compounds of the present invention are described hereinbelow.

Reference Example 1 Preparation of 2-f luoro-6-trif luoromethylbenzamidoxime - In 540ml of methanol was d isso lved 58.8g of hyd r oxy 1 am i ne hydrochloride and to the solution was added 160ml of aqueous solution of sodium carbonate containing 49.4g thereof. 40 of 2-f luoro-6-t r i f 1 uorome thy 1 benzon i t r i 1 e was added thereto at room temperature with stirring, and then further stirred 3 hours at 60» C. After removing the solvent methanol by distillation from the solution, the solution was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and it was concentrated under reduced pressure, thereby obtaining crude crystals. The crystals were then added with 200ml of 3N aqueous solution of hydrochloric acid and thoroughly stirred, then the insoluble substance resulted in the solution was removed by f i ltration. The f i ltrate was then neutral ized with 10% aqueous solution of sodium hydroxide under cooling and then extracted again with ethyl acetate. The organic layer was dried over anhydrous mag'nesium sulfate, and the solution was concentrated under reduced pressure to obtain 26.6g of the objective compound, m. p. 155-157°C The examples of benzamide oxime derivatives represented by the general formula [V], which can be manufactured according to the methods as described above, are given in Table 1 hereinbelow.

Table 1.

Chemical formula X2 X3 V V , Physical const.

H H H H mp 124-126eC H H H CI mp 112-115°C H H CI F mp 107-108°C 24. 0 H H CI CI nD 1.5210 H H H F mp 155-157°C H H F F mp 105-107°C H H F CI mp 98- 99°C H H CF3 CI mp 97- 99°C Reference Example 2 Preparation of N' -cyclopropy l ethy loxy-2-f luoro-6-trif luoromethy lbenzami dine In 100ml of DMF was dissolved 26.6g of 2-f 1 uoro-6- 1 r i f 1 uorome thy 1-benzamidoxime and 17.8 of cyclopropylmethylbromide, and to the solution was added 4.8g of sodium hydride (60¾ in oil) at 10 °C over 30 min. The solution was then stirred for 3 hours, and the solution reacted was poured into ice-water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure and the residue was subjected to silica gel column chromatography to obtain 24.8g of the objective compound, m. p. 63-64°C Reference Examples 3 Preparation of N' -eye lopropy 1methyl oxy-3, 6-bistr if luoromethy 1-2-chloro-benzamid ine Preparation of N' -eye 1 opropy Irae thy 1 oxy-3, 6-bistrifluoromethyl-2-chloro benzamid ine In 10ml of chloroform was dissolved 0.60g of 3, 6-bistrif luoromethyl- 2-chlorobenzamidoxime and 0.50g of cyclopropy lmethy lbromide, and to the sol ut ion was added O. lg of t e t ra bu t y 1 ammon i um bromi de at room temperature with stirring, and then 1.2ml of 10% aqueous solution of sodiumhydroxide, then stirred for 3 hours at 30-40, C. The solution was washed with water, washed with saturated saline solution and dried over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure and the residue was subjected to sil ica gel column chromatography to obtain 0.40g of the objective compound. m. p. 75-80°C The examples of benzami dox ime derivatives represented by the general formula [II], which can be prepared according to the methods similar to the methods as described above, are given in Table 2 hereinbelow.

- Table 2.

Chemical formula X2 X3 X4 X5. R1 Physical const. 24. 5 H H H H CH2cPr nD 1.4917 H H H F Et mp 64-66°C 24. 0 H H H F iPr nD 1.4789 H H H F CH2C(CH3) 3 mp 97-98°C 23. 5 H H H F CH2C≡CH nD 1.5011 H H H CI CHzcPr mp 43-46°C H H CI F CHzcPr mp 71-73°C 23. S H H CI CI CH2C≡CH nD 1.5360 23 S CI H H CI CH2cPr nD ' 1.5308 H H CI CI CH2cPr mp 73-75eC H H F F CH2cPr mp 43-45°C H H F CI CH2cPr mp 54-55°C H H CFs CI CHzcPr mp 75-78°C * cPr represnts cyclopropylmethy1 in the tables.

Now, the representative examples for the compounds of the present invention, which can be manufactured according to the praparation methods similar to the ones described in Examples 1 and 2, are given in Tables 3 and 4. However, it should be noted that X1, X2, X3, X\ X5, R1, R2, ri and r2 given in the Tables 3 and 4 correspond to X1, X2, X3, X4, Xs, R\ R2, rt and r2 given for the compounds represented by the general formula [Γ], respectively.

Table 3. (r1, r2 =H) Table 3 (continued) Table 3 (continued) Table 3 (continued) Physical const.

No. X1 X2 X3 X4 X5 R1 R2 mp. (°C) refractive index 93 CF3 H H H CI CH.cPr 3-methyl- -2-thienyl 94 CF3 H H H CI CH2cPr . 4-methyl- -2-thienyl 95 CF3 H H H CI CH2cPr 5-methyl- -2-thienyl 96 CF3 H H H CI CHzcPr 2-thienyl 47-49 97 CF3 H H H CI CH2cPr 4-methyl- -3-thienyl 98 CF3 H H H CI CH2cPr 5-methyl- -3-thienyl 99 CF3 H H H CI CH2cPr 3-thienyl 74-76 100 CF3 H H H CI CH2cPr Ph-2, 4-F2 101 CF3 H H H CI CH.cPr Ph-2-F 102 CF3 H H H CI CH.cPr Ph-2-F-3-Me 103 CF3 H H H CI CH.cPr Ph-2-F-4-0Me 104 CF3 H H H CI CH2cPr Ph-2-P-4-0Me- -5-Me 23. 8 105 CF3 H H H CI CH2cPr Ph-2-F-5-Me no 1.5323 106 CF3 H H H CI CH2cPr Ph-3, 5-Me2 107 CF3 H H H CI CH2cPr Ph-3-Me 108 CF3 H H H CI CH2cPr Ph-3-Me-4-F 109 CF3 H H H CI CH2cPr Ph-3-Me-4-0Me 110 CF3 H . H H CI CH2cPr Ph-4-F 111 CF3 H H H CI CH2cPr Ph-4-Me 112 CF3 H H H CI CH.cPr Ph-4-0Me 65-67 113 CF3 H H H CI CH2cPr Ph 63-65 114 CF3 H H H CI CH2C≡CH Ph-4-0Me 76-78 115 CF3 H H H CI CH2C≡CH Ph 96-97 Table 3 (continued) Table 3 (continued) Physical const.

No. X1 X2 X3 X4 X5 R1 R2 mp. (°C) refractive index 139 CF3 H H H CF3 CH2cPr 5-methyl- -2-thienyl 22. 4 140 CF3 H H H CF3 CH2cPr 2-thienyl n D 1.5082 141 CF3 H H H CF3 CH2cPr 4-methyi -3-thienyl 142 CF3 H H H CF3 CH2cPr 5-methyl- -3-thienyl 143 CF3 H H H CF3 CH2cPr 3-thienyl 144 CF3 H H H CF3 CH2cPr Ph-2.4-F2 145 CF3 H H H CF3 CH2cPr Ph-2-F 146 CF3 H H H CF3 CH2cPr Ph-2-F-3-Me 147 CF3 H H H CF3 CH2cPr Ph-2-F-4-0Me 148 CF3 H H H CF3 CH2cPr Ph-2-F-4-0Me- -5-Me 149 CF3 H H H CF3 CH2cPr Ph-2-F-5-Me 74 -75 150 CF3 H H H CF3 CH2cPr Ph-3, 5-Me2 151 CF3 H H H CF3 CH2cPr Ph-3-Me 152 CF3 H H H CF3 CH2cPr Ph-3-Me-4-F 153 CF3 H H H CF3 CH2cPr - Ph-3-Me-4-0Me 154 CF3 H H H CF3 CH.cPr Ph-4-F 155 CF3 H H H CF3 CH2cPr Ph-4-Me 22. 8 156 CF3 H H H CF3 CH2cPr Ph-4-0Me nD 1.5031 157 CF3 H H H CF3 CH2cPr Ph 68-69 158 CF3 H H H CF3 CH2C≡CH Ph-4-0Me 159 CF3 H H H CF3 CH2C≡CI . Ph-4-0Me 160 CF3 H H H CF3 iPr Ph-4-0Me 161 CF3 H H H CF3 nBu Ph-4-0Me Table 3 (continued) (r1, r2 =H) Table 3 (continued) 1 Physical const.

No. X1 X2 X3 X4 Xs R1 R2 mp. (°C) refractive index 185 CF3 H H H OMe CH.cPr 5-methyl- -3-thienyl 186 CF3 H H H OMe CH2cPr 3-thienyl 187 CF3 H H H OMe CH2cPr Ph-2,4-F2 188 CF3 H H H OMe CH2cPr Ph-2-F 189 CF3 H H H OMe CH2cPr Ph-2-F-3-Me 190 CF3 H H H OMe CH2cPr Ph-2-F-4-0Me 191 CF8 H H H OMe CH2cPr Ph-2-F-4-0Me- -5-Me 192 CF3 H H H OMe CH2cPr Ph-2-F-5-Me 193 CF3 H H H OMe CH.cPr Ph-3, 5-Me2 194 CF3 H H H OMe CH2cPr Ph-3-Me 195 CF3 H H H OMe CH2cPr Ph-3-Me-4-F 196 CF3 H H H OMe CH2cPr Ph-3-Me-4-0Me 197 CF3 H H H OMe CH2cPr Ph-4-F 198 CF3 H H H OMe CH2cPr Ph-4-Me 199 CF3 H H H OMe CH2cPr Ph-4-0Me 92-93 200 CF3 H H H OMe CH2cPr Ph-3-Cl-4-0Me 201 CF3 H H H OMe CH2cPr Ph-3-Cl-4-0Me- -5-Me 202 CF3 H H H OMe CH2cPr Ph 203 CF3 H H H OMe CH2C≡CH Ph-4-0Me 204 CF3 H H H OMe CH2C≡CI Ph-4-0Me 205 CF3 H H H OMe iPr Ph-4-0Me 206 CF3 H H H OMe nBu . Ph-4-0Me 207 CF3 H H H OMe nPr Ph-4-0Me Table 3 (continued) Table 3 (continued) Table 3 (continued) physical const, No. X1 X2 X3 X4 X5 Rl R2 mp. (°C) refractive index 254 CF3 H H CI F CH2cPr 5-methyl- -2-thienyl 255 CF3 H H CI F CH2cPr 2-thieny1 112-113 256 CF3 H H CI F CHzcPr 4-methyl- -3-thienyl 257 CF3 H H CI F CH2cPr 5-methyl- -3-thienyl 258 CF3 H H CI F CH2cPr 3-thieny1 125-126 259 CF3 H H CI F CH2cPr Ph-2,4-F2 260 CF3 H H CI F CH2cPr Ph-2-F 57-59 261 CF3 H H CI F CH2cPr Ph-2:F-3-Me 26. 7 262 CF3 H H CI F CH2cPr Ph-2F-4-0Me no 1.5200 263 CF3 H H CI F CH2cPr Ph-2-F-4-0Me- 73-74 -5-Me 264 CF3 H H CI F CH2cPr Ph-2-F-5-e 60-62 265 CF3 H H CI , F CH2cPr Ph-3, 5-Me2 266 CF3 H H CI F CH2cPr Ph-3-Me 92-93 267 CF3 H H CI F CH2cPr Ph-3-Me-4-F 98-99 268 CF3 H H CI F CH.cPr Ph-3-Me-4-0e 86-87 269 CF3 H H CI F CH2cPr Ph-4-F 94-95 270 CF3 H H CI F CH2cPr Ph-4-Me 75-76 271 CF3 H H CI F CH2cPr Ph-40Me 98 272 CF3 H H CI F CH.cPr Ph 112 273 CF3 H H CI F CH2C≡CH Ph 54-58 274 CF3 H H CI F CH2C≡CH Ph-2-F-5-Me 91-92 275 CF3 H H CI F CH2C≡CH Ph-4-0e 102-103 276 CF3 H H CI F CH2C≡CI Ph-4-0Me 112-114 Table 3 (continued) Table 3 (continued) physical const, No. X1 ' X2 X3 x4i X5 R1 R2 mp. (°C) refractive index 300 CF3 H H CI CI CH2cPr pyrazol-l-yl 301 CF3 H H CI CI CH.cPr 3-methyl- -2-thienyl 302 CF3 H H CI CI CH2cPr 4-methyl- -2-thienyl 303 CF3 H H CI CI CHzcPr 5-methyl- -2-thienyl 304 CF3 H H CI CI CH2cPr 2-thienyl 139-141 305 CF3 H H CI CI CH.cPr 4-methyl- -3-thieny1 306 CF3 H H CI CI CH2cPr 5-methyl- -3-thienyl 307 CF3 H H CI CI CH2cPr 3-thienyl 140-141 308 CF3 H H CI CI CH2cPr Ph-2, 4-F2 23. 0 309 CF3 H H CI CI CH.cPr Ph-2-F no 1.5404 310 CF3 H H CI CI CH.cPr Ph-2-F-3-Me 22 5 311 CF3 H H CI CI CH2cPr Ph-2-F-4-0Me no ' 1.5371 23. 5 312 CF3 H H CI CI CH2cPr' Ph-2F-4-0Me- nD 1.5287 -5-Me 313 CF3 H H CI CI CH2cPr Ph-2-F-5-Me 56-57 314 CF3 H H CI CI CH2cPr Ph-3, 5-Me2 315 CF3 H H CI CI CH2cPr Ph-3-Me 111-114 316 CF3 H H CI CI CH2cPr Ph-3-Me-4-F 113-114 317 CF3 H H CI CI CH.cPr Ph-3-Me-4-0Me 318 CF3 H H CI CI CH2cPr Ph-4-F 319 CF3 H H CI CI CH2cPr Ph-4-Me 93-95 320 CF3 H H CI CI CH.cPr Ph-4-0Me 97-98 321 CF3 H H CI CI CH2cPr Ph 134-135 322 CF3 H H CI CI CH2C≡CH Ph 96-98 Table 3 (continued) physical const, No. X1 X2 X3 X4 Xs R1 R2 mp. (°C) refractive index 323 CF3 H H CI CI CH2C≡CH Ph-2-F-5-Me 77-79 324 CF3 H H CI CI CH2C≡CH Ph-4-0Me 94-96 325 CF3 H H CI CI CH2C≡CI Ph-4-OMe 326 CF3 H H CI CI iPr Ph-4-0Me 123-124 327 CF3 H H CI CI nBu Ph-4-0Me 328 CF3 H H CI CI nPr Ph-4-0Me 88-89 329 CF3 H H CI CI tBu Ph-4-0Me 330 CF3 H H SMe F CH2cPr Ph-4-0Me 114-115 331 CF3 H H OMe F CH2cPr Ph-4-0Me 125-126 332 CF3 H H OMe F CH2cPr Ph-4-0Me 135-136 333 CF3 H H Me F CH2cPr Ph-4-0Me 71-72 334 CF3 H F H H Et Ph-4-0Me 70-72 335 CF3 H F H H" Me Ph-4-0Me 336 CF3 H F H H CH2cPr Ph-4-0Me 97-99 337 CF3 H F H H CH2cPr Ph 117-119 338 CF3 H F H H nBu Ph-4-0Me 339 CF3 H F H H tBu Ph 340 CF3 H CI H H Et Ph-4-0Me 89-91 341 CF3 H CI H H Me Ph-4-0Me 342 CF3 H CI H H CH2cPr Ph-4-0Me 97-99 343 CF3 H CI H H CH2cPr Ph 91-92 344 CF3 H CI H H nBu Ph-4-0Me 345 CF3 H CI H H tBu Ph Table 3 (continued) Table 3 (continued) physical const, No. X1 X2 X3 X" X5 R1 1 R2 mp. CO refractive index 369 CF3 H H F F CH2cPr Ph-3, 5-Me2 370 CF3 H H F F CH2cPr Ph-3-Me 70-72 371 CF3 H H F F CH.cPr Ph-3-Me-4-F 51-53 372 CF3 H H F F CH2cPr Ph-3-Me-4-0Me 56-57 373 CF3 H H F F CH2cPr Ph-4-F 70-72 374 CF3 H H F F CH2cPr Ph-4-Me 64-66 375 CF3 H H F F CH.cPr Ph-4-0Me 73-74 376 CF3 H H F F CH2cPr Ph 61-62 377 CF3 H H F F CH2C≡CH Ph 76-78 378 CF3 H H F F CH2C≡CH Ph-2-F-5-Me 84-86 379 CF3 H H F F CH2C≡CH Ph-4-0Me 100-102 380 CF3 H . H F F CH2C≡CI Ph-4-0Me 381 CF3 H H F F iPr Ph-4-0Me 65-66 382 CF3 H H F F nBu Ph-4-0Me 383 CF3 H H F F nPr Ph-4-0Me 67-69 384 CF3 H H F F tBu Ph-4-0Me 385 CF3. H H F F CH2cPr 5-methyl- -2-thienyl 386 CF3 H H F F CH2cPr 2-thieny1 69-71 387 CF3 H H F F CH2cPr 4-methyl- -3-thienyl 388 CF3 H H F F CH2cPr 5-methyl- -3-thienyl 389 CF3 H H F F CH2cPr 3-thienyl 79-81 390 CF3 H H F F CH2cPr Ph-2, 4-F2 Table 3 (continued) Table 3 (continued) Table 3 (continued) physical const.

No. X1 X2 X3 X4 X9 R1 R2 mp. (°C) refractive index 436 CF3 H H F CI CH2cPr 3-methyl- -pyrazol-l-yl 437 CF3 H H F CI CH2cPr 4-methyl- -pyrazol-l-yl 438 CF3 H H F CI CH2cPr pyrazol-l-yl 439 CF3 H H F CI CH.cPr 3-methyl- -2-thienyl 440 CF3 H H F CI CHzcPr 4-methyl- -2-thieny1 441 CF3 H H F CI CHzcPr 5-methyI- -2-thienyl 442 CF3 H H F CI CH2cPr 2-thienyl 104-106 443 CF3 H H F CI CH.cPr 4-methyl- -3-thienyl 444 CF3 H H F CI CH2cPr 5-methyl- -3-thieny1 445 CF3 H H F CI CH.cPr 3-thienyl 113-115 446 CF3 H H . F CI CH2cPr Ph-2, 4-F2 23. 8 447 CF3 H H F CI CH2cPr Ph-2-F n D 1.5262 448 CF3 H H F CI CH2cPr Ph-2-F-3-Me 449 CF3 H H F CI CH2cPr Ph-2-F-4-0Me 450. CF3 H H F CI CH2cPr Ph-2-F-4-0Me- -5-e 451 CF3 H H F CI CH2cPr Ph-2-F-5-Me 62-63 452 CF3 H H F CI CH2cPr Ph-3, 5-Me2 453 CF3 H H F CI CH2cPr Ph-3-Me 96-98 454 CF3 H H F CI CH2cPr Ph-3-Me-4-F 82-83 455 CF3 H H F CI CH2cPr Ph-3-Me-4-0Me 72-73 456 CF3 H H F CI CHzcPr Ph-4-F 76-77 457 CF3 H H F CI CH.cPr Ph-4-Me 75-76 458 CF3 H H F CI CH2cPr Ph-4-0Me 68-69 Table 3 (continued) physical const.

No. X1 X2 X3 X4 Xs R1 R2 mp. (°C) refractive index 459 CF3 H H F CI CH2cPr Ph 102-104 460 CF3 H H F CI CH2C ≡CH Ph 461 CF3 H H F CI CHzC ≡CH Ph-4-0Me 462 CF3 H H F CI CH2C ≡CH Ph-2-F-5-Me 463 CF3 H H F CI CH2C ≡CI Ph-4-0Me 464 CF3 H H F CI iPr Ph 465 CF3 H H F CI iPr Ph-4-0e 466 CF3 H H F CI iPr Ph-2-F-5-Me 467 CF3 H H F CI nPr Ph 468 CF3 H H F CI nPr Ph-4-0Me 469 CF3 H H F CI nPr Ph-2-F-5-Me 470 CF3 H H F CI nBu Ph-4-0Me 471 CF3 H H F CI tBu Ph-4-0e 472 CF3 H H CF3 CI CH2CH=CH2 Ph 473 CF3 H H CF3 CI CH2CH=CH2 Ph-4-0Me 474 CF3 H H CF3 CI CH2CH=CH2 Ph-2-F-5-Me 475 CF3 H H CF3 CI CH2CH3 . Ph 476 CF3 H H CF3 CI CH2CH3 Ph-4-0Me 477 CP's H H CF3 CI CH2CH3 Ph-2-F-5-Me 478 CF3 H H CF3 CI CH2CH2CI Ph 479 CF3 H H CF3 CI CH2CH2C1 Ph-4-0Me 480 CF3 H H CF3 CI CH2CH2C1 Ph-2-F-5-Me 481 CF3 H H CF3 CI CH3 Ph Table 3 (continued) No. X1 X2 χ3 | physical const.

X4 Xs R1 R2 mp. (°C) refractive index 482 CF3 H H CF3 CI CH3 Ph-4-0Me 483 CF3 H H CF3 CI CH3 Ph-2-F-5-Me 484 CF3 H H CF3 CI CH20Me Ph-4-0Me 485 CF3 H H CF3 CI CH2cPr 3-methyl- -pyrazol-l-yl 486 CF3 H H CF3 CI CH2cPr 4-methy1- -pyrazo1-1-yl 487 CF3 H H CF3 CI CH2cPr pyrazol-l-yl 488 CF3 H H CF3 CI CH2cPr 3-methyl- -2-thienyl 489 CF3 H H CF3 CI CH2cPr 4-methy1- -2-thienyl 490 CF3 H H CF3 CI CH2cPr 5-methy1- -2-thienyl 491 CF3 H H CF3 CI CH2cPr 2-thienyl 492 CF3 H H CF3 CI CH2cPr 4-methyl- -3-thienyl 493 CF3 H H CF3 CI CH2cPr 5-methy1- -3-thienyl 494 CF3 H H CF3 CI CH2cPr 3-thienyl 495 CF3 H H CF3 CI CH2cPr Ph-2, 4-F2 496 CF3 H H CF3 CI CH2cPr Ph-2-F 497 CF3 H H CF3 CI CH2cPr Ph-2-F-3-Me 498 CF3 H H CF3 CI CH2cPr Ph-2-F-4-0Me 499 CF3 H H CF3 CI CH2cPr Ph-2-F-4-0Me- -5-Me 500 CF3 H H CF3 CI CH2cPr Ph-2-F-5-Me 501 CF3 H H CF3 CI CH2cPr Ph-3, 5-Me2 502 CF3 H H CF3 CI CH2cPr Ph-3-Me 503 CF3 H H CF3 CI CH2cPr Ph-3-Me-4-F 504 CF3 H H CF3 CI CH.cPr Ph-3-Me-4-0Me Table 3 (continued) physical const.

No. X1 X2 X3 X4 X5 R1 R2 mp. (°C) refractive index 505 CF3 H H CF3 CI CH2cPr Ph-4-F 506 CF3 H H CF3 CI CH2cPr Ph-4-Me 507 CF3 H H CF3 CI CH2cPr Ph-4-0Me 508 CF3 H H CF3 CI CHzcPr Ph 65-67 509 CF3 H H CF3 CI CH2C≡CH Ph 510 CF3 H H CF3 CI CH2C≡CH Ph-4-0Me 511 CF3 H H CF3 CI CH2C≡CH Ph-2-F-5-Me 512 CF3 H H CF3 CI CH2C≡CI Ph 513 CF3 H H CF3 CI iPr Ph 514 CF3 H H CF3 CI iPr Ph-4-0Me 515 CF3 H H CF3 CI iPr Ph-2-F-5-Me 516 CF3 H H CF3 CI nPr Ph 517 CF3 H H CPs CI nPr Ph-4-0Me 518 CF3 H H CF3 CI nPr Ph-2-F-5-e 519 CF3 H H CF3 CI nBu Ph-4-0Me 520 CF3 H H CF3 CI tBu Ph-4-0Me 521 CF3 H H CF3 F CH2CH=CH2 Ph 522 CF3 H H CF3 F CH2CH=CH2 Ph-4-0Me 523 CF3 H H CF3 F CH2CH=CH2 Ph-2-F-5-e 524 CF3 H H CF3 F CH2CH3 Ph 525 CF3 H H CF3 F CH2CH3 Ph-4-0Me 526 CF3 H H · CF3 F CH2CH3 Ph-2-F-5--Me 527 CF3 H H CF3 F CH2CH2C1 Ph Table 3 (continued) physical const.

No. X1 X2 X3 X4 X9 R1 R2 mp. (°C) refractive index 528 CF3 H H CF3 F CH2CH2C1 Ph-4-0Me 529 CF3 H H CF3 F CH2CH2c1 Ph-2-F-5-Me 530 CF3 H H CF3 F CH3 Ph 531 CF3 H H CF3 F CH3 Ph-4-0Me 532 CF3 H H CF3 F CH3 Ph-2-F-5-Me 533 CF3 H H CF3 F CH20Me Ph-4-0Me 534 CF3 H H CF3 F CH2cPr 3-methyl- -2-thienyl 535 CF3 H H CF3 F CH2cPr 4-methyl- -2-thienyl 536 CF3 H H CF3 F CH.cPr 5-methyl- -2-thienyl 537 CF3 H H CF3 F CH2cPr 2-thienyl 538 CF3 H H CF3 F CH2cPr 4-methyl- -3-thienyl 539 CF3 H H CF3 F CH2cPr 5-methyl- -3-thienyl 540 CF3 H H CF3 F CH2cPr 3-thienyl 541 CF3 H H CF3 F CH2cPr 4-methyl- -3-thienyl 542 CF3 H H CF3 F CH2cPr 5-methyl- -3-thienyl 543 CF3 H H CF3 F CH2cPr 3-thienyl 544 CF3 H H CF3 F CH2cPr . Ph-2, 4-F2 545 CF3 H H CF3 F CH2cPr Ph-2-F 546 CF3 H H CF3 F CH2cPr Ph-2-F-3-Me 547 CF3 H H CF3 F CH2cPr Ph-2-F-4-0Me 548 CF3 H H CF3 F CH2cPr Ph-2-F-4-0Me- -5-Me 549 CF3 H H CF3 F CH2cPr Ph-2-F-5-Me 550 CF3 H H CF3 F CH2cPr Ph-3, 5-Me2 Table 3 (continued) physical' const.

No. X1 X2 X3 X4 X5 R. ! R2 mp. (°C) refractive index 551 CF3 H H CF3 F CH2cPr Ph-3-Me 552 CF3 H H CF3 F CH2cPr Ph-3-Me-4-F 553 CF3 H H CF3 F CH2cPr Ph-3-Me-4-0Me 554 CF3 H H CF3 F CH2cPr Ph-4-F 555 CF3 H H CF3 F CH2cPr Ph-4-Me 556 CF3 H H CF3 F CH2cPr Ph-4-0Me 557 CF3 H H CF3 F CH2cPr Ph 558 CF3 H H CF3 F CH2C≡CH Ph 559 CF3 H H CF3 F CH2C≡CH Ph-4-0Me 560 CF3 H H CF3 F CH2C≡CH Ph-2-F-5-Me 561 CF3 H H CF3 F CH2C≡CI Ph-4-0Me 562 CF3 H H CF3 F iPr Ph 563 CF3 H H CF3 F iPr Ph-4-0Me 564 CF3 H H CF3 F iPr Ph-2-F-5-Me 565 CF3 H H CF3 F nPr Ph 566 CF3 H H CF3 F nPr Ph-4-0Me 567 CF3 H H CF3 F nPr Ph-2-F-5-Me 568 CF3 H H CF3 F nBu Ph-4-0Me 569 CF3 H H CF3 F tBu Ph-4-0Me. 570 CF3 F H H CI CH2cPr Ph 571 CF3 F H H CI CH2cPr Ph-4-0Me 572 CF3 F H H CI CH2cPr Ph-2-F-5-Me 573 CF3 F H H F CH2cPr Ph Table 3 (continued) physical const.

No. X1 X2 X3 X4 X5 Rl R2 mp. CO refractive index 574 CF3 F H H F CH2cPr Ph-4-0Me 575 CF3 F H H F CH2cPr Ph-2-F-5-Me 576 CF3 CF3 H H CI CH2cPr Ph 577 CF3 CF3 H H CI CH2cPr Ph-4-0Me 578 CF3 CF3 H H CI CHacPr Ph-2-F-5-Me 579 CF3 CF3 H H F CH2cPr Ph 580 CF3 CF3 H H F CH2cPr Ph-4-0Me 581 CF3 CF3 H H F CH2cPr Ph-2-F-5-Me 582 CF3 CI H H CF3 CH2cPr Ph 583 CF3 CI H H CF3 CH2cPr Ph-4-0Me 584 CF3 CI H H CF3 CH2cPr Ph-2-F-5-Me 585 CF3 F H H CF3 CH2cPr Ph 586 CF3 F H H CF3 CH2cPr Ph-4-0Me 587 CF3 F H H CF3 CH2cPr Ph-2-F-5-e 588 CF3 CF3 H H CF3 CH2cPr Ph 589 CF3 CF3 H H CF3 CH2cPr Ph-4-0Me 590 CF3 CF3 H H CF3 CH2cPr Ph-2-F-5-Me 591 CF3 H H H CH3 CH2cPr Ph 592 CF3 H H H CH3 CH2cPr Ph-4-0Me 593 CF3 H H H CH3 CH2cPr Ph-2-F-5-Me 594 CF3 H H F CH3 CH2cPr Ph 595 CF3 H H F CH3 CH2cPr Ph-4-0Me 596 CF3 H H F CH3 CH2cPr Ph-2-F-5-Me Table 3 (continued) physical const.

No. X1 X2 X3 X4 X5 R1 R2 mp. (°C) refractive index 597 CF3 H H CI CH3 CH2cPr Ph 598 CF3 H H CI CH3 CH2cPr Ph-4-0Me 599 CF3 H H CI CH3 CHzcPr Ph-2-F-5-Me 600 CF3 F H F F CH.cPr Ph 601 CF3 F H F F CH2cPr Ph-4-0Me 602 CF3 F H F F CH2cPr Ph-2-F-5-Me 603 CF3 F H F CI CHzcPr Ph 604 CF3 F H F CI CH2cPr Ph-4-0Me 605 CF3 F H F CI CH.cPr Ph-2-F-5-Me 606 CF3 F H CI F CH2cPr Ph 607 CF3 F H CI F CH2cPr Ph-4-0Me 608 CF3 F H CI F CH2cPr Ph-2-F-5-e 609 CF3 F H CI CI CH.cPr Ph 610 CF3 F H CI CI CH.cPr Ph-4-0Me 611 CF3 F H CI CI CH.cPr Ph-2-F-5-Me 612 CF3 CI H F F CH.cPr Ph 613 CF3 CI H F F CH2cPr Ph-4-0Me 614 CF3 CI H F F CH2cPr Ph-2-F-5-Me 615 CF3 CI H F CI CH2cPr Ph 616 CF3 CI H F CI CH2cPr Ph-4-0Me 617 CF3 CI H F CI CH2cPr Ph-2-F-5-Me 618 CF3 CI H CI F CH2cPr Ph 619 CF3 CI H CI F CH2cPr Ph-4-0Me Table 3 (continued) physical const.

No. X1 X2 X3 X4 X5 R1 R2 mp. (°C) refractive index 620 CF3 CI H CI F CH2cPr Ph-2-F-5-Me 621 CF3 CI H CI CI CH2cPr Ph 622 CF3 CI H CI CI CH.cPr Ph-4-0Me 623 CF3 CI H CI CI CH2cPr Ph-2-F-5-Me 624 CF3 CI H CI CF3 CHzcPr Ph 625 CF3 CI H F CF3 CH2cPr Ph 626 CF3 F H CI CF3 CH2cPr Ph 627 CF3 F H F CF3 CH2cPr Ph 628 CF3 CF3 H CI CI CH2cPr Ph 629 CF3 CF3 H CI F CH2cPr Ph 630 CF3 CF3 H F CI CH2cPr Ph 631 CF3 CF3 H F F CH2cPr Ph 632 CF3 CI H CF3 CI CH2cPr Ph 633 CF3 F H CF3 CI CH2cPr Ph 634 CF3 CI H CF3 F CH2cPr Ph 635 CF3 F H CF3 F CH2cPr Ph 636 CF3 CF3 H CI CF3 CH2cPr Ph 637 CF3 CF3 H F CF3 CH2cPr Ph 638 CF3 CF3 H CF3 CF3 CHzcPr Ph 639 CF3 F F F F CH2cPr Ph 640 CF3 F F F CI CH2cPr Ph 641 CF3 F F CI F CH2cPr Ph 642 CF3 F F CI CI CH2cPr Ph Table 3 (continued) physical const.

No. X1 X2 X3 X4 X5 R1 R2 mp. CC) refractive index 643 CF3 CI H CI CF3 CH.cPr Ph-4-0Me 644 CF3 CI H F CF3 CH2cPr Ph-4-0Me 645 CF3 F H CI CF3 CH2cPr Ph-4-0Me 646 CF3 F H F CF3 CH2cPr Ph-4-0Me 647 CF3 CF3 H CI CI CH2cPr Ph-4-0e 648 CF3 CF3 H CI F CH.cPr Ph-4-0Me 649 CF3 CF3 H F CI CHzcPr Ph-4-0Me 650 CF3 CF3 H F F CH2cPr Ph-4-0Me 651 CF3 CI H CF3 CI CH2cPr Ph-4-0Me 652 CF3 F H CF3 CI CH2cPr Ph-4-0Me 653 CF3 CI H CF3 F CH.cPr Ph-4-0Me 654 CF3 F H CF3 F CH2cPr Ph-4-0Me 655 CF3 CF3 H CI CF3 CH2cPr Ph-4-0Me 656 CF3 CF3 H F CF3 CH2cPr Ph-4-0Me 657 CF3 CF3 H CF3 CF3 CH2cPr Ph-4-0Me 658 CF3 F F F F CH.cPr Ph-4-0Me 659 CF3 F F F CI CH2cPr Ph-4-0Me 660 CF3 F F CI F CH2cPr Ph-4-0Me 661 CF3 F F CI CI CH2cPr Ph-4-0Me 662 CF3 H H H F CH2-l-F-cPr Ph 663 CF3 H H H F CH2-2-F-cPr Ph 664 CF3 H H H F CH2-2-F2-cPr Ph 665 CF3 H H H . F CH2-l-F-cPr Ph-4-0Me Table 3 (continued) physical const.

No. X1 X2 X3 X4 X5 R1 R2 mp. (°C) refractive index 666 CF3 H H H F CH2-2-F-cPr Ph-4-0Me 667 CF3 H H H F CH2-2-F2-cPr Ph-4-0Me 668 CF3 H H CI CI CHz-l-F-cPr Ph 669 CF3 H H CI CI CH2-2-F-cPr Ph 670 CF3 H H CI CI CH2-2-F2-cPr Ph 671 CF3 H H CI CI CH2-l-F-cPr Ph-4-0Me 672 CF3 H H CI CI CH2-2-F-cPr Ph-4-0e 673 CF3 H H CI CI CH2-2-F2-cPr Ph-4-0Me 674 CF3 H H CI F CHVl-F-cPr Ph 675 CF3 H H CI F CH2-2-F-cPr Ph 676 CF3 H H CI F CHV2-F2-cPr Ph 677 CF3 H H CI F CHz-l-F-cPr Ph-4-0Me 678 CF3 H H CI F CH2-2-F-cPr Ph-4-0Me 679 CF3 H H CI F CH2-2-F2-cPr Ph-4-0Me 680 CF3 H H F CI CHz-l-F-cPr Ph 681 CF3 H H F CI CH2-2-F-cPr Ph 682 CF3 H H F CI CH2-2-F2-cPr Ph 683 CF3 H H F CI CH2-l-F-cPr Ph-4-0Me 684 CF3 H H F CI CH2-2-F-cPr Ph-4-0Me 685 CF3 H H F CI CH2-2-F2-cPr Ph-4-0Me 686 CF3 H H F F CHVl-F-cPr Ph 687 CF3 H H F F CH2-2-F-cPr Ph 688 CF3 H H F F CH2-2-F2-cPr Ph Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Physical const, No. X1 X2 X3 X4 X3 R1 R2 mp (°C) (refractive index) 875 CF3 H H H F CH2cPr Ph-4-0CF2CF3 876 CF3 H H H F CH2cPr Ph-4-0CF2CF2H 877 CF3 H H H F CH2cPr l-Me-2-Pyrrolyl 878 CF3 H H H F CH2cPr l-Me-3-Pyrrolyl 879 CF3 H H H F CH.cPr 2-Pyrrolyl 880 CF3 H H H F CH2cPr 3-Pyrrolyl 881 CF3 H H F F CH2cPr Ph-2-Cl 882 CF3 H H F F CH2cPr Ph-4-Br 883 CF3 H H F F CH.cPr Ph-2-Cl-4-F 884 CF3 H H F F CH2cPr ■ Ph-2-Br-4-CH3 885 CF3 H H F F CH2cPr Ph-4-Et 886 CF3 H H F F CH2cPr Ph-4-0Et 887 ' CF3 H H F F CH2cPr- Ph-4-0iPr 888 CF3 H H F F CH2cPr Ph-4-0CH2CH=CH2 889 CF3 H H F F CH.cPr Ph-4-0CH2C≡CH 890 CF3 H H F F CH.cPr Ph-3-CF3 891 CF3 H H F F- CH.cPr Ph-4-CF3 892 CF3 H H F F CH.cPr Ph-4-CF2CF2H 893 CF3 H H F F CH2cPr Ph-4-0CF3 894 CF3 H H F F CH2cPr Ph-4-OCFzH 895 CF3 H H F F CH2cPr Ph-4-0CF2CF3 896 CF3 H H F F CH.cPr Ph-4-0CF2CF2H 897 CF3 H H F F CH2cPr l-Me-2-Pyrrolyl 898 CF3 H H F F CH2cPr l-Me-3-Pyrrolyl Table 3 (continued) Physical const.

No. X1 X2 X3 X4 X5 R1 R2 1 rap (°C) (refractive index) 899 CF3 H H F F CH2cPr .2-Pyrrolyl 900 CF3 H H F F CH2cPr 3-Pyrrolyl 22. 0 901 CF3 H H F Br CH2cPr Ph nD , 1.5349 902 CF3 H H H Et CH2cPr Ph 903 CF3 H H H nPr CH2cPr Ph 904 CF3 H H H nBu CH.cPr Ph 905 CF3 H H H tBu CH2cPr Ph 906 CF3 H H H C2F5 CH2cPr Ph 907 CF3 H H H OEt CHicPr Ph 908 CF3 H H H OnPr CH2cPr Ph 909 CF3 H H H OiPr CH2cPr Ph ■ 910 CF3 H H H OtBu CH2cPr Ph 911 CF3 H H OBt F CH2cPr Ph 912 CF3 H H OnPr F CH2cPr Ph 913 CF3 H H OiPr F CHzcPr Ph 914 CF3 H H OtBu F CH2cPr Ph 23. 3 915 CF3 H H . H SOMe CH2cPr Ph nD ' 1.5450 916 CF3 H H H S02Me CH2cPr Ph 144-146 917 CF3 H H H SEt CH2cPr Ph 918 CF3 H H H S-iPr CH2cPr Ph 919 CF3 H H SOMe F CH2cPr Ph 920 CF3 H H SO.Me F CH2cPr Ph 921 CF3 H H SEt F CH2cPr Ph 922 CF3 H H S-iPr F CH2cPr Ph Table 3 (continued) Physical const, No. X1 X2 X3 1 X4 Xs R1 R2 mp CO (refractive index) 923 CF3 H H 0CF3 F CH.cPr Ph-4-0e 924 CF3 H H 0CF3 F CH2cPr Ph-2-F 925 CF3 H H 0CF3 F CH2cPr Ph-4-F 926 CF3 H H 0CF3 F CHzcPr Ph 927 CF3 H H N02 0CH3 CH2cPr Ph 928 CF3 H H NHAc F CH2cPr Ph 929 CF3 H H NH. F CH2cPr Ph 930 CF3 H H F F CHzCOOH Ph 113-120 931 CF3 H H- F F CH2cPr 2-imidazolyl • l-methyl-2- 932 CF3 H H F F CH2cPr -imidazolyl l-meth l-2- 933 CF3 H H F F CH2cPr -oxazolyl 934 CF3 H H F F CH2cPr 2-isoxazolyl l-methyl-2- . 935 CF3 H H F F CH2cPr -isoxazolyl 936 CF3 H H F F CH2cPr 2-pyrimidiny1 937 CF3 H H F F CHzcPr 4, 6-dimethyl-2 -pyrimidinyl 938 CF3 H H F F CH2cPr 2-thiazolyl 939 CF3 H H F F CHzcPr 3-chloro-2- -thiazolyl 940 CF3 H H F F CH2cPr 1-pyrazinyl 941 CF3 H H F F ' CH2cPr 3-mrthyl-l- -pyrazinyl 942 CF3 H H F F CH2cPr 3-pyridaziny1 943 CF3 H H F F CHzcPr 3-methyl-4- -pyridazinyl 944 CF3 H H F F CH2cPr 2-furyl 945 CF3 . H H F F CH2cPr 3-bromo-2- -furyl 946 CF3 H H F F CH2cPr 4-thiazolyl CH2-l-F-cPr : CH2-2-F-cPr : CH2-2-F2-cPr : CH2-l-Cl-cPr : CH2-cHex-3,4-Br2: -CH2 -Br CH2-cPent:-CH2 \__7 Table 4.

No. X1 X2 X3 X4 X5 R1 ri r2 R2 Physical const, mp. (°C)/ refractive index 947 CF3 H H F F CH2cPr OMe H Ph 25.4-1.5069 948 CF3 H H F F CH2cPr Me H Ph 25.5-1.5106 949 CF3 H H F F CH.cPr Et H Ph 25.4-1.5003 950 CF3 H H F F CH2cPr OMe CF3 Ph 25.5-1.4855 951 CF3 H H F F CH2cPr F H Ph 25.5-1.5059 952 CF3 H H F F CH2cPr CI H Ph 25.5-1.5244 953 CF3 H H F F CH2cPr SMe H Ph 25.5-1.5220 954 CF3 H H F F CH2cPr = 0 Ph 79-81 955 CF3 H H F F CH2cPr Me Me Ph 25.6-1.5105 956 CF3 H H F F CH2cPr F F Ph 50-52 957 CF3 H H F F CH2cPr NHMe H Ph 958 CF3 H H CI F CH2cPr OMe H Ph 959 CF3 H H CI F CH2cPr Me H Ph 960 CF3 H H CI F CH2cPr Et H Ph 961 CF3 H H CI F CH2cPr OMe CF3 Ph 962 CF3 H H CI F CH2cPr F H Ph 963 CF3 H H CI F CH2cPr CI H Ph 964 CFa H H CI F CH2cPr SMe H Ph 965 CF3 H H CI F CH.cPr =0 Ph Table 4 (continued) No. X1 X2 X3 X4 Xs R ' | r i r2 R2 Physical const, mp. (°C)/ refractive index 966 CF3 H H CI F CH.cPr Me Me Ph 967 CF3 H H CI F CH2cPr F F Ph 968 CF3 H H CI F CHzcPr NHMe H Ph 969 CF3 H H F CI CHzcPr OMe H Ph 970 CF3 H H F CI CH2cPr Me H Ph 971 CF3 H H F CI CH2cPr Et H Ph 972 CF3 H H F CI CH2cPr OMe CF3 Ph 973 CF3 H H F CI CHzcPr F H Ph 974 CF3 H H F CI CHzcPr CI H Ph 975 CF3 H H F CI CH.cPr SMe H Ph 976 CF3 H H F CI CH.cPr = 0 Ph 977 CF3 H H F CI CH2cPr Me Me Ph 978 CF3 H H F CI CH2cPr F F Ph 979 CF3 H H F CI CH2cPr NHMe H Ph 980 CF3 H H CI CI CH.cPr OMe H Ph 981 CF3 H H CI CI CH.cPr Me H Ph 982 CF3 H H CI CI CH2cPr Et H Ph 983 CF3 H H CI CI CH2cPr OMe CF3 Ph 984 CF3 H H CI CI CH2cPr F H Ph 985 CF3 H H CI CI CH2cPr CI H Ph 986 CF3 H H CI CI CH2cPr SMe H Ph 987 CF3 H H CI CI CH2cPr = 0 Ph 988 CF3 H H CI CI CH2cPr Me Me Ph 989 CF3 H H CI CI CH2cPr F F Ph 990 CF3 H H CI CI CH2cPr NHMe H Ph Table 4 (continued) Table 4 (continued) 23. 4 *25.4—1.5069 means nD 1.5069 (refractive index) in the above tables. Ή-NMR data (CDC13. δ ppm from TMS) ; *1 Compound No. 346 | 0.1 -0.2 (2H, m), 0.45 -0.55 (2H, m), 0.95-1.1 (1H, m), 3.60 (2H, s), 3.8-3.9 (2H, m), 3.82 (3H, s), 6.92 (2H, d), 7.1-7.25 (3H, m), 7.51 (1H, dd), 8.53 (1H, brs) The compounds of the present invention can show excellent fungicidal activity against wide varieties of fungi, and therefore, the compounds can be useful for plant disease control in the farming of agricultural and horticultural crops including ornamental flowers, turf and forage crops.

The examples for the plant diseases to be controlled with the compounds of the present invention are given in the following.

Paddy rice Blast (Pyricularia oryzae) Sheath blight (Rhizoctonia solani) Bakanae disease (Gibberella fujikuroi) Helminthospor ium leaf spot (Coch 1 iobo 1 us miyabeanus) Barley Loose smut (Ustilago nuda) Wheat Scab (Gibbere 1 la zeae) Leaf rust (Puccinia recondita) Eye spot (Pseudocercosporella herpotrichoides) Glume blotch (Leptosphaeria nodorum) Powdery mi Idew (Erysiphe graminis f. sp. tritici) Fusarium snow blight (Micronectriel la nivalis) Potato Late blight (Phytophthora infestans) Ground nut Leaf spot (Mycosphaere 1 la arad Sugar beat Cercospora leaf (Cercospora beticola) spot Cucumber Powdery mildew (Sphaerotheca fuliginea) Sclerotinia rot (Sclerotinia sclerot iorum) Gray mold (Botrytis cinerea) Downy mi ldew (Pseudoperonospora cubensis) Tomato Leaf mold (Cladospor iu fulvum) Late blight (Phytophthora infestans) Egg plant Black rot (Corynespora melongenae) Onion Gray-mold neck rot (Botrytis allii) Strawberry Powdery mildew (Sphaerotheca humuli) Apple Powdery mi ldew (Podosphaera leucotricha) Scab (Venturia inaequalis) Blossom blight (Monilinia mali) Pers immon Anthracnose (Gloeosporium kaki) Peach Brown rot (Monilinia fructicola) Grape Powdery mildew (Uncinula necator) Downy mildew (Plasmopara viticola) - - Rust (Gymnosporang ium asiaticum)- Black spot (Alternaria kikuchiana) Tea-plant Leaf spot (Pestalotia theae) Anthracnose (Co 11eto t r i chum theae-s inens is) Orange Scab (Elsinoe fawcetti) Blue mold (Penici 11 ium i tali cum) Turf Sclerotinia snow blight (Sclerotinia borealis) In recent years, it is known that various pathogenic fungi have developed their resistance to benz imidazo le fungicides and ergosterol biosynthesis inhibitors and that such fungicides have been insufficient in their fungicidal effectiveness. Therefore, it is required to provide new compounds useful as a fungicide which are effective to the resistant-strain of such pathogenic fungi as well. The compounds of the present invention are the ones which can be a fungicide having excellent fungicidal effectiveness not only to the susceptible-strains of pathogenic fungi but also to the resistant-strains of pathogenic fungi to benz imi dazole fungicides and ergosterol biosynthesis inhibitors.

For the preferable examples of plant diseases to be applied with the compounds of the present invention, powdery mildew on wheat, powdery mildew on cucumber, powdery mildew on strawberries, etc. can be given.

The compounds of the present invention can be utilized as an antifouling agent for preventing the adhesion of aqueous organisms to structures, such as the bottom of a ship and fishing nets, in water and sea.

Also, the compounds of the present invention can be contained in paints and fibers and thereby used as an antimicrobial agent for walls, bathtubs, shoes and clothes. \ Furthermore, some of the compounds of the present invention can show i nsec t i c i da 1, acaricidal and herbicidal activities.

In the practical application of the compounds of the present invention obtained as described above, the compounds can be used in the state as it is without formulation, or, for the use as agricultural plant protection chemicals, the compounds can be applied in forms of general formulations for agricultural plant protection chemicals, such as wettable powders, granules, powders, emulsifiable concentrates, aqueous solutions, suspensions and flowables. For the additives and carriers to be used in the formulations described above, vegetable powders, such as soybean powder and wheat powder, mineral fine powders, such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay, and organic and inorganic compounds, such as sodium benzoate, urea and Glauber' s salt, can be used, when the compounds are formulated into solid formulations. Whereas, when the compounds are formulated into liquid formulations, petroleum fractions, such as kerosine, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethyl formamide, dimethyl sulfoxide, alcohols, acetone, trichloro ethylene, methyl isobutyl ketone, mineral oils, vegetable oils and water, can be used as the solvent. In these formulations, surface active agents may be added to the formulations in order to make the formulations homogeneous and stable, if appropriate.

The content of the compound of the present invention as the active principle in the formulations is preferably in a range of from 5 to 70%.

The wettable powders, the emulsifiable concentrates and the flowable formulation comprising the compound of the present invention prepared as described above can be applied in a form prepared by diluting the formulations with water to the suspension or the emulsion at a desired concentrations, while the powders and the granules of the said compound can be directly applied to plants without dilution.

The compounds of the present invention can demonstrate sufficient effectiveness on plant diseases independently, however, it is also possible to use the said compound in admixing with 1 or more of other fungicides, insecticides, acaricides or synergists.

The followings are the examples for the fungicides, insecticides, acaricides, nematocides and plant growth regulators, those which are usable in admixing with the compounds of the present invention.

Fungicides: Copper-based fungicides: Basic copper chloride, basic copper sulfate, etc.

Sulphur-based fungicides: Thiram, maneb, mancozeb, po lycarbamate, propineb, ziram, zineb, etc. Polyhaloalky 1 thio fungicides: Captan, dichlof luanid, folpet, etc.

Organochlor ine fungicides: Chlorotha Ion i 1. fthalide, etc.

Organophosphorous fungicides: IBP, EDDP, to 1clofos-methy 1, pyrazophos, fosetyl-Al, etc.

Benzimidazole fungicides: Thiophanate-methy 1, benomyl, carbendazim, thiabendazole, etc.

Dicarboxyimide fungicides: Oxycarboxine, mepronyl, flutolanil, tech'lof thalam, trichlamide, pencycuron, etc.

Acyl alanine fungicides: Metalaxyl, oxadixyl, furalaxyl etc.

EBI fungicides: - - Triadiraefon, triadomenol, bitertanol, mi crobu tan i 1 , hexaconazol, propiconazole, trif lumizole, procloraz, peflazoate, fenarimol, pyrifenox, trifolin, flusilazole, etaconazole, d i c 1 obu t razo 1 , fluotrimazole, flutriafen, penconazole, d i n i conazo 1 e. cy roconazo 1 e, imazalil, tridemorph, fenpropimorph, buthiobate, etc.

Antibiotics: Polyoxin, blast icidin-S, kasugamycin, val i damyc in, streptomycin sulfate, etc.

Others : Propamocarb hydrochloride salt, quintozene, hyd rox i soxa zo 1 e, metasulfocarb, anilazine, isoprothiolane, probenazole, qu inomethionate, dithianone, dinocap, dichlomezine, mepaniprim, ferimzone, fluazinam, pyroquilon, t r i eye 1 azo 1 e, oxolinic acid, dithianone, iminoctazine acetate salt, cymoxanil, pyrroleni trine, metasulfocarb, diethofencarb, binapacryl, lecithin, sodium hydrogencarbonate, fenaminosu 1 f, dodine, dimethomorph, fenazine oxide, etc.

Insecticides and Acaricides: Organophosphorous and carbamate insecticides: Fenthion, fenitrothion, diazinon, chlorpyr ifos, ESP, vamidothion, fenthoate, dimethoate, formothion, malathon, trichlorfon, thiometon, phosmet, dichlorvos, acephate, EPBP, methyl parathion, oxydimeton methyl, ethion, salithion, cyanophos, isoxathion, pyr i dafen th i on, phosalon, me t hy da t h i on, sulprofos, c h 1 o r f e nv i np ho s , t e t r a c h 1 o r v i np ho s , d ime thy 1 v i nphos, propaphos, isofenphos, ethyl thiometon, profenofos, pyraclophos, monocro tophos, azinphos methyl, aldicarb, me thorny I, thiodicarb, carbofuran, carbosulfan, benfuracarb, furathiocarb, propoxur, BPMC, MTMC, M1PC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, cartap, thiocyclam, bensultap, etc.

Pyrethroid insecticides: Permethrin, cypermet'hr in, del tamethrin, fenvalerate, fenpropathr in, pyrethrin, allethrin, tel rame thr in, resmethr in, dimethrin, propathrin, fenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothr in, f lucythrinate, ethofenprox, eye 1 opro t hr i n, tralomethr in, s i 1 af 1 uophen, brofenprox, acrinathr in, etc.

Benzoyl urea-based insecticides and others: D i f 1 u ben z u ron, ch 1 o r f 1 ua z u ron, h exa f 1 umu ron, triflumuron, tetrabenzuron, f 1 ufenoxuron, f lucycloxuron, buprofezin, pyr iproxyfen, methoprene, benzoepin, diaphenthiuron, imidaclopr id, fipronil, nicotine sulfate, rotenone, me ta-a 1 dehyde, machine oil, Bacillus thur ingiensis, microbial insecticides such as insect-pathogenic viruses, etc.

Nematoc ides : Fenamiphos, phosthiazate, etc.

Acaricides: Chlorbenz i late, phenisobromolate, dicofol, amitraz, BPPS, benzomate, hexythiazox, fenbutatin oxide, polynactin, qu inomethionate, CPCBS, tetradifon, avermectin, milbemectin, chlofentezin, cyhexatin, pyridaben, fenpyroxymate, tebufenpyrad, pyrimidifen, fenothiocarb, dienochlor, etc. Plant Growth Regulators: Gibbere 11 ines (Gibberel 1 ine A3, Gibberelline A , Gibberelline A?, etc. ), IAA, and NAA.

Now, the examples of the formulations comprising the compound of the present invention are described hereinbelow, however, it should be noted that the type and the rate of the additives shall not be limited to the ones described in the examples and can be replaced by wide range of other additives and/or carriers. In the examples hereinbelow, a part mentioned in each of the formulation examples represents a part by weight.

Example 3 : Wettable Powder The compound of the present invention 40 parts D iatomaceous earth 53 parts Sulfuric acid ester of higher alcohol 4 parts Alkyl naphthalene sulfonate 3 parts All components are admixed and micronized to fine powder, thereby affording the wettable powder formulation containing the active principle at a concentration of 40%.

Example 4 : Emulsifiable Concentrate The compound of the present invention 30 parts Xylene 33 parts Dimethyl formamide 30 parts Polyoxy ethlene alkylally ether 7 parts All components are admixed and then dissolved into a solution, thereby affording the emulsifiable concentrate formulation containing the active principle at a concentration of 30%.

Example 5 : Dust Formulation The compound of the present invention 10 parts Talc 89 parts Polyoxy ethlene alkylally ether 1 parts All components are admixed and pulverized to fine dusting powder, thereby affording the dust formulation containing the active principle at a concentration of 10%.

Example 6 : Granular Formulation The compound of the present invention 5 parts Clay ' 73 parts Bentonite 20 parts Sodium salt of dioctylsulfosuccinate 1 part - - Sodium phosphate 1 part All components are admixed, pulverized and then kneaded thoroughly while adding water, and then further granulated and dried, thereby affording the granular formulation containing the active principle at a concentration of 5%.

Example 7 : Suspension The compound of the present invention . 10 parts Sodium lignin sulfonate 4 parts Sodium dodecyl benzene sulfonate 1 part Xanthane Gum 0.2 part Water 84.8 parts All components are admixed and subjected to wet grinding up to the particle size of less than 1 , thereby affording the suspension containing the active principle at a concentration of 10%.

Now, the usefulness of the compounds of the present invention as the active principle of a plant protection chemical for controlling various plant diseases is shown in Test Examples described hereinbelow. The effectiveness of the compounds, on plant disease control were assessed basing on the pathological changes in the state of plants provided, namely the degree of disease-induced lesion on leaves, stems and other parts of the plants was visually observed, respectively. The assessment was conducted by giving scores in effectiveness on lant diseases to each test plots as the following.

Score, 5; If no lesion were observed.

Score, 4; If the degree of the lesion observed were approximately 10% of the degree in the untreated plot.

Score, 3; If the degree of the lesion observed were approximately 25% of the degree in the untreated plot.

- Score, 2; If the degree of the lesion observed were approximately 50¾ of the degree in the untreated plot. ( Score, 1; If the degree of the lesion observed were approximately 75% of the degree in the untreated plot.

Score, 0; If the degree of the lesion observed were almost same as the degree in the untreated plot.

Test Example 1 : Preventive Control Eff icacy Test on Wheat Powdery Mi ldew To young seedlings of wheat (Variety: Chihoku) grown in an unglazed pot, the emulsion at a concentration of 12.5 ppm prepared from the emulsif iable concentrate comprising the compound of the present invention were sprayed throughly. After the spraying, the seedlings were dried under natural condition and then inoculated by means of sprinkling with the conidia of the fungus causing wheat powdery mildew (Erysiphe graminia f. sp. tr i t ici) and placed in a greenhouse maintained at around 20 °C for 7 days in order to complete the infection. Appearance of the lesion on leaves cause by the disease was assessed and compared with the lesion on leaves in the untreated plot, thereby evaluating the preventive efficacy of the compound to the disease. The results are shown in Table 5.

Test Example 2 : Preventive Control Eff icacy Test on Cucumber Powdery Mildew To young seedlings of cucumber (Variety: Sagami-Han j i ro) grown in an unglazed pot, the emulsion at a concentration of 12.5 ppm prepared from the emulsif iable concentrate comprising the compound of the present invention were sprayed. After the spraying, the seedlings were dried under natural condition and then inoculated by means of sprinkling wi th the conidia of the fungus causing cucumber powdery mi ldew (Sphae ro theca fuliginea) and placed in a temperature-controlled room maintained at around 25 °C for 11 days in order to complete the infection.. Appearance of powdery mildew-causing lesion on the leaves whereto the compound was sprayed was assessed and compared with the lesion appeared on leaves in the untreated plot, thereby evaluating the preventive efficacy of the compound to the disease. The results are shown in Table 5.

As shown in Table 5, it is demonstrated that the compounds of the present invention can show superior preventive control efficacy to not only wheat powdery mildew but also cucumber powdery mildew in comparison with other compounds tested.

Test Example 3 : Test on Cucumber Powdery Mildew Control with Vapour 10 1 of the emulsion at a concentration of 500 ppm prepared from the emulsifiable concentrate comprising the compound of the present invention were fed dropwise onto' round aluminium foils each having a diameter of 1 cm and dried at room temperature under natural condition.

The aluminium foils were then fixed on the upper side of the leaves of cucumber seedlings (Variety: Sagami-Hanj iro) grown in an unglazed pot. After 24 hours, the cucumber leaves were inoculated by means of sprinkling with the conidia of the fungus causing cucumber powdery mildew (Sphaerotheca fuliginea) and placed in a temperature-controlled room maintained at around 25°C for 11 days in order to complete the infection. Appearance of powdery mildew-causing lesion on the leaves placed with the aluminium foil was assessed and compared with the lesion appeared on the leaves in the untreated plot. The control efficacy with the vapour of the compound to the disease was confirmed in case that disease lesion-free circle having a diameter of more than 2 cm is formed around the aluminium foil fixed on a leaf. The results are shown in Table 5.

On the other hand, other compounds for the comparison, which are disclosed in Japanese Patent Laid-opened No. Hei 2-6453 (see Table 5). did not show the control efficacy with the vapour to the disease.

Since the compounds of the present invention have vapour action, it is suggested that the compound of the present invention can show plant disease control efficacy even in the inner space of leaves and fruits of crops whereto spraying of a fungicide in even condition is generally rather difficult.

- - Table 5.

Concentrat ion Wheat Cucumber Vapar of active Powdery Powdery act ion ingredient mi Idew mi Idew (ppm) 12.5 5 5 12.5 5 5 12.5 5 5 12.5 5 5 12.5 : 5 5 12.5 4 5 12.5 5 5 12.5 5 5 12.5 4 5 12.5 5 5 12.5 5 5 12.5 5 5 12.5 2 4 12.5 4 5 12.5 4 5 12.5 5 5 12.5 5 5 good 12.5 5 5 12.5 5 5 12.5 4 4 Table 5 (continued) Concentrat ion Wheat Cucumber Vapar of active Powdery Powdery action ingredient mi Idew mi Idew (ppm) 12.5 4 4 12.5 5 4 12.5 4 4 12.5 3 5 12.5 4 5 good 12.5 5 5 good 12.5 5 4 12.5 4 5 good 12.5 5 4 12.5 5 5 good 12.5 5 5 good 12.5 5 5 good 12.5 5 5 good 12.5 4 4 12.5 5 5 12.5 5 5 good 12.5 5 5 good 12.5 5 5 12.5 5 5 good 12.5 5 5 good 12.5 5 5 good 12.5 5 5 12.5 5 5 good 12.5 5 5 " Table 5 (continued) Concentrat ion Wheat Cucumber Vapar of active Powdery Powdery act ion ingredient mi Idew mi Idew (ppm) 12.5 5 5 good 12.5 5 5 good 12.5 4 4 12.5 4 4 12.5 4 5 12.5 4 5 12.5 4 4 12.5 5 5 12.5 5 5 12.5 5 5 12.5 - 5 4 12.5 5 5 12.5 5 5 12.5 5 5 good 12.5 5 5 good 12.5 5 5 good 12.5 5 5 good 12.5 5 5 good 12.5 4 5 12.5 4 5 12.5 3 5 ■ good Table 5 (continued) Concentration Wheat Cucumber Vapar No. of active Powdery Powdery act ion ingredient mi Idew mi Idew (ppm) 149 12.5 5 5 good 156 12.5 5 5 good 157 12.5 5 5 good 209 12.5 4 4 211 12.5 4 4 212 12.5 5 5 234 12.5 5 5 good 239 12.5 5 5 good 240 12.5 5 5 good 241 12.5 5 5 good 242 12.5 5 5 good 255 .12.5 5 5 good 258 12.5 5 5 good 260 12.5 5 5 good 262 12.5 5 5 good 263 12.5 5 5 264 12.5 5 5 good 266 12.5 5 5 267 12.5 5 5 good 268 12.5 5 5 269 12.5 5 5 good 270 12.5 5 5 good 271 12.5 5 5 Table 5 (continued) Concentrat ion Wheat Cucumber Vapar No. of active Powdery Powdery act ion ingredient mi Idew mi Idew (ppm) 272 12.5 5 5 good 273 12.5 5 5 good 274 12.5 5 5 275 12.5 5 5 276 12.5 5 4 277 12.5 5 5 279 12.5 5 5 good 280 12.5 5 5 286 12.5 5 5 287 12.5 5 5 288 12.5 ■ 5 5 · 289 12.5 5 5 290 12.5 5 5 good 293 12.5 4 5 304 12.5 5 5 307 12.5 5 5 309 12.5 5 5 good 311 12.5 5 5 good 312 12.5 5 5 313 12.5 5 5 good Table 5 (continued) Concentrat ion Wheat Cucumber Vapar No. of active Powdery Powdery action ingredient mi Idew mi Idew (ppm) 315 12.5 5 5 316 12.5 5 5 319 12.5 5 5 good 320 12.5 5 5 321 12.5 5 5 322 12.5 5 5 323 12.5 5 5 324 12.5 4 4 326 ■ 12.5 5 5 328 12.5 5 5 good 333 12.5 5 5 good 346 12.5 5 4 347 12.5 4 4 348 12.5 3 4 349 12.5 4 5 351 12.5 5 4 good 352 12.5 5 4 good 353 12.5 5 4 good Table 5 (continued) Concentrat ion Wheat Cucumber Vapar No. of active Powdery Powdery act ion ingredient mi Idew mi Idew (ppm) 364 12.5 5 5 good 367 12.5 5 5 good 368 12.5 5 5 good 370 12.5 5 5 good 371 12.5 5 5 good 372 12.5 5 5 good 373 12.5 5 5 good 374 12.5 5 5 good 375 12.5 5 5 good 376 12.5 5 5 good 377 12.5 5 5 good 378 12.5 5 5 379 12.5 5 5 good 381 12.5 5 5 good 383 12.5 5 5 good 386 12.5 5 5 good 389 12.5 5 •5 good 391 12.5 5 5 392 12.5 5 5 good Table 5 (crjnt inued) Concentrat ion Wheat Cucumber Vapar No. of active Powdery Powdery action ingredient mi Idew mi Idew (ppm) 393 12.5 5 5 good 395 12.5 '5 5 good 396 12.5 5 5 good 399 12.5 4 5 400 12.5 5 5 401 12.5 5 5 good 402 12.5 5 5 good 403 12.5 5 5 good 404 12.5 5 5 good 405 12.5 5 5 good 406 12.5 5 5 good 407 12.5 5 5 good 408 12.5 5 5 good 409 12.5 5 5 410 12.5 5 5 413 12.5 5 5 good 414 12.5 5 5 good 415 12.5 5 5 good 429 12.5 5 Table 5 (continued) Concentrat ion Wheat Cucumber Vapar No. of active Powdery Powdery act ion ingredient mi Idew mi Idew (ppm) 430 12.5 5 442 12.5 5 5 good 445 12.5 5 5 good 447 12.5 5 5 good 451 12.5 5 5 good 453 12.5 5 5 good 454 12.5 5 5 good 455 12.5 5 5 good 456 12.5 5 5 good 457 12.5 5 5 good 458 12.5 5 5 good 459 12.5 5 5 good 508 12.5 5 5 694 12.5 5 861 12.5 4 868 12.5 4 937 12.5 4 Reference : 12.5 5 1 Industrial Ap licability: The compounds of the present invention have excellent fungicidal effectiveness, and therefore, are useful as a fungicide for agricultural and horticultural use.

All passages of the description, which are not within the scope of the claims, do not form part of the invention.

Claims (3)

117864/2 What is claimed is;

1. Benzamidoxime derivatives represented by the formula ll'l wherein R 1 is straight-chain or branched d .- C alkyl ; a group represented 'by a general formula, R3CH2, wherein R 3 is a group selected from a group consisting of d - C8 cycloalkyl, '■ Ct. - d haloalkyl, Ct -C3 . alkoxy, C i - C3 alkyl thio, C i - C3 alkylsulf inyl, C i - C3 a lkylsu lf onyl, d - C3 alkoxycarbonyl, cya o, amino, C i - C3 monoa 1 ky 1 a i o, Ci - C3 d i a 1 ky 1 am i no, acylamino and cyano; d - d alkeny 1 or C2 - C alkynyl, ■ R2 is phenyl optionally having one or more substituents selected from a group consisting of halogen, d - C3 alkyl, Ci - C3 alkoxy, Ci - C3 haloalkyl and d - C3 haloalkoxy; or a heterocycle group selected from pyrazolyl or thienyl which are optionally substituted by Q - C4 alkyl, X1 is Ci - d haloalkyl, . X'2, X3, X4 and X5 are each independently hydrogen, halogen, Ci - C4 alkyl, d .-. C4 haloalkyl, Ci - C4 alkoxy, Ci - C4 haloalkoxy, Ci - C4 alky 1 thio, Ci. - G4 alkylsulf inyl, Ci - C4 alkylsulfonyl, nitro, amino or Ci - C4 alky lcarbonylamino, and ri and r2 are each independently hydrogen,, halogen, Ci - C4 alkyl, Ci ' - C4 haloalkyl, Ci - C4 alkoxy, d - C4 alky 1 thio or amino, or ri and r2 may form carbonyl in together. 117864/3

2. A process for preparation of benzamidoxime der ivat ives represented by the formula [I1]; wherein R1, X1, X2, X3, X4,' Xs, R2, r.i and rz are as described above, which comprises reacting a compound represented by the formula [II] whe e, with a compound represented by the formula [III]; whe r∑ are as described above.

3. A f ung i c i de f or agr i cu ltural and hort icul tural, use, characterized in that the fungici de comprises one or more of the benzamidoxime derivatives represented by the formula [i ; wherein R1,' X1, X2, X3, X4, Xs, R2, ri .and. r2 are as described above, as the active principle.