FLUOROVINYLOXYACETAMIDES, PROCESS FOR PREPARING SAME AND HERBICIDAL COMPOSITION COMPRISING SAME

Abstract: Herbicidal fluorovinyloxyacetamide compounds of formula (I) are useful for protecting crops from weeds, wherein: R<1> is a phenyl group optionally having one or more substituents selected from the group consisting of C1-6 alkyl, halogen-substituted C1-6 alkyl, C1-6 alkoxy and halogen; R<2> is a C1-6 alkyl; or R<1> and R<2> together with the nitrogen atom to which they are bound form a 5-, 6- or 7-membered nitrogen heterocycle optionally having one or more ring oxygen atoms, double bonds and C1-6 alkyl substituents; R<3> is a phenyl or thiophen-2-yl group optionally having one or more substituents selected form the group consisting of C1-6 alkyl, halogen-substituted C1-6 alkyl, C1-6 alkoxy, methylenedioxy and halogen; and R<4> is a perfluoro C1-6 alkyl group.

Description: - 1 - FLUOROVINYLOXYACETAMIDES, PROCESS FOR PREPARING SAME AND HERBICIDAL COMPOSITION COMPRISING S.AME Field of the Invention The present invention relates to novel fluorovinyloxyacetamides, a process for preparing same and a highly selective and effective herbicidal composition comprising same. Description of the Prior Art Due to the perpetual emergence of weeds resistant to the herbicide in use, there always exists a need to develop a new class of effective herbicides that can protect crops without harming the environment. For example, the sulfonylurea-based herbicides that have been widely used in controlling rice-field weeds for the last two decades have now become less effective, particularly in controlling annual weeds. Accordingly, many attempts have been made to develop new rice-field herbicides of different chemical classes, including those based on amides and carbamates. There has recently been reported a new class of herbicides based on heteroaryloxyacetamide derivatives (DE Patent No. 2903966; DE Patent No. 3038636; DE Patent No. 3323334; DE Patent No. 3344236; DE Patent No. 3418167; DE Patent No. 3422861; DE Patent No. 440596; WO 95/34560; WO 96/08488; WO 96/11575; WO 96/28434; and WO 97/08160). However, these heteroaryloxyacetamides have limited herbicidal activity against a narrow spectrum of weeds. Summary of the Invention Accordingly, it is a primary object of the present invention to provide a novel compound having superior herbicidal activity against a wide spectrum of weeds. It is another object of the present invention to - 2 - provide a process for the preparation of said compound. It is a further object of the present invention to provide a herbicidal composition comprising said compound. In accordance with one aspect of the present invention, there is provided a novel fluorovinyloxyacetamide compound of formula ( I ) : 0 R 1 R N-C-CH 2 0-CF=CR 3 R A (I! wherein: R 1 is a phenyl group optionally having one or more substituents selected from the group consisting of C 1-6 alkyl, halogen-substituted C 1-6 alkyl, C 1 _ 6 alkoxy and halogen; R 2 is a C 1 _ 6 alkyl group; or R 1 and R 2 together with the nitrogen atom to which they are bound form a 5-, 6- or 7-membered nitrogen heterocycle optionally having one or more ring oxygen atoms, double bonds and C.,_ 6 alkyl substituents; R 3 is a phenyl or thiophen-2-yl group optionally having one or more substituents selected from the group consisting of C 1-6 alkyl, halogen-substituted C 1.6 alkyl, C,_ 6 alkoxy, methylenedioxy and halogen; and R 4 is a perfluoro C 1-6 alkyl group. Detailed Description of the Invention The compound of formula (I) of the present invention may be in the form of the E isomer of formula (I-a), the Z. isomer of formula (I-b), or a mixture thereof: - 3 - E isomer (I-a) Z. isomer (I-b) wherein R 1 , R 2 , R 3 and R 4 have the same meanings as defined in formula (I) above. The two stereoisomers , E. and Z. isomers, are defined according to the terminology of the Cahn-Ingold-Prelog system(J. March, Advanced Organic Chemistry, 3rd Ed., Wiley-Interscience ) which is incorporated herein by way of reference. Among the compounds of the present invention, preferred are: those wherein R 1 is a phenyl group optionally having a halogen, methyl or methoxy substituent, R 2 is a methyl or i- propyl group, R 3 is a phenyl group optionally substituted with a halogen or methoxy group and R A is CF 3 or CF 2 CF 3 ; and those wherein R 1 and R 2 together with the nitrogen atom to which they are bound form a piperidino, hexamethyleneimino, morphorino or 1 , 2 , 3 , 6-tetrahydropyridino ring optionally having one or two C-_ 2 alkyl substituents, R 3 is a phenyl group optionally substituted with a halogen or methoxy group and R A is CF 3 . The compound of the present invention may be prepared by reacting an alcoholic compound of formula (II) with a fluorovinyl compound of formula (III) in the presence of a base, as shown in Reaction Scheme A: - 4 - Reaction Scheme A o R >.A J^R 5 R 'RTJ-C-CH j O-CF-^CRTT Y Y II ~^OOHH + F T O R 4 (10 (III) (I) wherein R , R 2 , R 3 and R 4 have the same meanings as defined in formula (I) above. An alcoholic compound of formula (II) may be prepared by substitution, acetylation and hydrolysis of an amine of formula (VI) according to a conventional method(Hamm, P.C, J. er. Chem. Soc .. 78. 2556 (1956); Hartman, W.W. et al., Org. Syn.. Coll.. 2, 650 (1955); and Brasen, W.R. et al . , Org. Syn. , Coll. , A, 582 (1963)), as shown in Reaction Scheme B: Reaction Scheme B R1 substitution R 1 acetylation R 1 O hydrolysis R NH -'V'CJ tf-*γ c " F - ^H o O o O O II II ■ yi) C1CH 2 -C-C1 (V) CH j -C-ONa (|V) (II) wherein R 1 and R 2 have the same meanings as defined in formula (I) above. A difluorovinyl compound of formula (III) may be prepared form a halogen compound of formula (VIII) by Grignard and Wittig reactions (Herkes , F.E. et al., J. Org. Chem.. 32, 1311 (1967); and Wheaton, G.A. et al., J. Or . Chem. , 48, 917 (1983)), as shown in Reaction Scheme C: - 5 - Rea ction .Sr-hPτnP C. Grignard , Wittig reaction O-^^-R reaction R 3 X i ) Mg , THF I R-.4 * CF 2 Br 2 , PH.P (viii) U) R'-c-oEt (vn) wherein X is Br or Cl; and R 3 and R have the same meanings as defined in formula (I) above. As shown in Reaction Scheme A, the fluorovinyloxyacetamide compound of the present invention may be prepared by reacting an alcoholic compound of formula (II) with a fluorovinyl compound of formula (III) in the presence of a base. Each of compounds of formula (II) and (III) may be used in equimolar amounts and ' the base may be used in one to two equivalent amounts. The base may be an inorganic base, e.g., sodium hydride, potassium hydride, potassium t-butoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate; or an organic base, e.g., triethylamine or pyridine. The solvent which may be used in the reaction is benzene, toluene, tetrahydrofuran, acetone, acetonitrile, dichloromethane, dimethylformamide or dimethylsulfoxide, individually or combined with water. The reaction may be conducted at a temperature ranging from room temperature to 100 °C. The progress of the reaction is conveniently followed by measuring the disappearance of the compound of formula (II) with thin layer chromatography ( TLC ) . The compound of the present invention is obtained as a mixture of two isomers, i.e., the E and Z. isomers . For example, in the case of the compound of the present invention wherein R 1 is phenyl, R 2 is methyl, R 3 is phenyl and R 4 is CF 3 ( Compound 1), a 2:1 mixture of the Z. and E. isomers is obtained, the isomer ratio being determined on - 6 - the basis of both 1 H-NMR and 19 F-NMR analysis of the product. Namely, the peak area ratio of the 1 H-NMR peak for the methylene group of the Z. isomer (a singlet at 4.30 ppm relative to CHC1 3 ) to that of E . isomer (a singlet at 4.49 ppm) is about 2:1; and 19 F-NMR analysis (reference compound: CFC1 3 ) shows a peak area ratio of about 2:1 when the peaks for the fluorine and CF 3 substituents of the Z. isomer (a quartet having a coupling constant of 24.08 Hz at -84.99 ppm and a doublet having a coupling constant of 25.07 Hz at - 57.36 ppm, respectively) are compared with those of the E isomer (a quartet having a coupling constant of 12.43 Hz at - 83.40 ppm and a doublet having a coupling constant of 12.66 Hz at -57.95 ppm, respectively). Likewise, the preparation of the compound of the present invention wherein R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidino group, R 3 is phenyl and R 4 is CF 3 ( Compound 221) leads to a 2:1 mixture of the Z. and £ isomers. Namely, the peak area ratio of the 1 H-NMR peak for the methylene group of the Z, isomer (a singlet at 4.67 ppm) to that of the E isomer (a singlet 4.79 ppm) is about 2:1; and the 19 F-NMR analysis (reference compound: CFC1 3 ) shows a peak area ratio of 2:1 when the peaks for the fluorine and CF 3 substituent of the Z. isomer (a quartet having a coupling constant of 25.15 Hz at -84.28 ppm and a doublet having a coupling constant of 24.85 Hz at -57.38 ppm, respectively) are compared with those of the E . isomer (a quartet having a coupling constant of 12.46 Hz at -82.24 ppm and a doublet having a coupling constant of 12.32 Hz at -57.83 ppm, respectively). The compound of the present invention has herbicidal activity against a broad spectrum of weeds, in particular, against those belonging to the Gramineae family, e.g., rice(Oryza sativa L. ) , barnyardgrass (Echinochlora crus-galli 8P. BEAUV. var. oryzicola OHWI), bulrush( Scirpus juncoides ROXB), umbrellaplant (Cyperus difformis L. ) , flat- sedge (C_y^eL !lS _S r_oj£ini l s_ ROTTB ) , riayfl ower rAneilema keisak - 7 - HASSK), monochoria(Monochor vaginalis PRESL), toothcup(Rotala indica KOEHE ) and arrow headf Saσittaria pygmaea MIQ) . Accordingly, the present invention also includes within its scope a herbicidal composition comprising one or more of the compounds of formula (I) as an active ingredient, in association with herbicidally acceptable carriers. The herbicidal composition of the invention may be formulated in various forms such as an emulsion, aqueous dispersion, powder and granules which may contain herbicidally acceptable carriers and additives. The compound of the formula (I) may be used in an amount of 10 to 90 % on the basis of the weight of an emulsion or aqueous dispersion, 0.1 to 10% on the basis of the weight of powder, 1 to 30 % on the basis of the weight of granules. Herbicidally acceptable carrier that may be used in the composition of the present invention is a liquid carrier, e.g., water, an alcohol (ethanol , ethylene glycol, glycerine), ketone ( acetone , methylethy lketone ) , ether (dioxane, tetrahydrofuran, cellosolve), aliphatic hydroc arbon ( gasoline , Kerosene), halogenated hydrocarbon ( chloroform , carbon tetrachlor ide ) , amide ( dimethylformamide ) , ester (ethyl acetate, butyl acetate, fatty glycerine ester) and acetonitrile; and a solid carrier, e.g., mineral particle (Kaoline , clay, bentonite, dolomite, talc, silica, sand) and vegetable powder ( shrubs ) . The additive that may be used in the herbicidal composition of the present invention includes an emulsifier, adhesive, dispersion agent or permeating agent, e.g., nonionic, anionic or cationic interface active agent (fatty acid sodium salt, polyoxy alkyl ester, alkyl sulfonate ester). Further, an agrochemically active ingredient, e.g., an insecticide, fungicide, plant growth regulator, germicide, and fertilizer, may be added in the composition of the present invention. The following Preparations and Examples are given for the purpose of illustration only and are not intended to limit the scope of the invention. Preparation 1 : Preparation of IL- methyl-2- hydroxyacetanilide( II ) Step 1 : Preparation of N-methyl-2-chloroacetanilide(V) 10.7 g(0.1 mol) of M-methylaniline (VI ) was dissolved in 150 ml of dichloromethane containing 10.12 g(0.1 mol) of triethylamine, and 13.55 g(0.12 mol) of chloroacetylchloride was added dropwise thereto while cooling. The resulting solution was stirred at room temperature for 1 hour, and washed three times with water. The organic layer was dried and recrystallized in n-hexane to obtain 17.6 g(yield 96%) of the title compound as a yellowish brown solid. 1 H-NMR (CDC1 3 , TMS) δ: 7.68-7.12(m, 5H), 3.92(s, 2H), 3.45(s, 3H) MS (m/e): 183(M + , 37), 134(51), 106(100), 90(52), 51(59). m.p. : 61-62 °C Step 2 : Preparation of N-methyl-2-acetoxyacetanilide ( IV) 18.3 g( 0.1 mol) of the compound obtained in Step 1 was added to 50 ml of dry dimethylformamide (DMF) , and 9.8 g(0.12 mol) of sodium acetate was added thereto. The resulting solution was heated for 1 hour, cooled and 50 ml of water was added thereto. The resulting solution was extracted three times with ethyl acetate and the organic layer was dried. After removing the solvent, the residue was subjected to column chromatography using a mixture of n- hexane and ethyl acetate(9:l) as an eluent to obtain 19 g(yield 92 %) of the title compound as a liquid. 1 H-NMR (CDC1 3 , TMS) 6: 7.78-7.21(m, 5H), 4.48(s, 2H), 3.36(s, 3H), 2.21(s, 3H) MS (m/e): 207(M + , 8), 107(61), 77(30), 43(100) - 9 - Step 3 : Preparation of N-methyl-2-hydroxyacetanilide ( II ) 20.7 g(0.1 mol) of the compound obtained in Step 2 was added to 100 ml of methanol, and 4.8 g(0.12 mol) of sodium hydroxide was added slowly thereto. The resulting solution was refluxed with heating for 1 hour. The solvent was removed under a reduced pressure and 50 ml of water was added thereto. The resulting solution was extracted three times with ethyl acetate. The organic layer was dried, the solvent was removed and the residue was recrystallized in n- hexane to obtain 14 g(yield 85%) of the title compound as a white solid. 1 H-NMR (CDC1 3 , TMS) δ : 7.54-7.15 (m, 5H), 3.82(d, 2H), 3.38(t, IH), 3.32(s, 3H) MS (m/e): 165(M + , 34), 134(41), 106(100), 77(81) m.p.: 41-42 °C Preparations 2 to 31 The procedure of Preparation 1 was repeated to obtain compounds of formula (II) having various R 1 and R 2 groups, as in Table 1. The 1 H-NMR and MS analysis data and melting points of these compounds are also shown in Table 1. L in Table 1 represents liquid. - 10 - oc rs τ . rs oc V V- CN ? σv v~ © OC σ © ON c" 8 X © r- © o r- ^ (N -^ _ w ■ vO ( >/- © rs r- © IN 4 J It - - s -: o © v <N © © T e- j- — — T £ " rT o oc © X x v N vO — X — O _ ^ r- _ r- — oc rs r- r- — • c r- © r~ ON — — © © — — — — ( rs © rs rs r^ m rs oc ro c~ ≤f ~ rs oc _ r^ r*- (N T? m oc ro oc c oc oc ^ - ^^ c_ rs — rs (N c — rs ? " *?- OC r_~ sC — w- vC 5c ro oc r- ~ oc ~ o c as— Z m <* " r~ c c- 5 ^^ f- rs — oc c ! Q \r OC S ~ NO ' Io — © ~^ *— " r- I ϋ ) vO ( ! r- O NO _* r-~ __- . - i i 1 1 I rs vO OC ©" u~ oc </~ oc © I ∑ C m rs W~ ON — r- rs m r- — I oc O Mr ON ON c — oc — VO I I I I I I i — — oc -v" © r-- oc oc r~ © oc — i ~ Tt O U u υ u u u u u u u u as . = ~ — I ^ ~ S X I I'u * . * u u u Λ u u υ * u u" υ U o a. Ό ^ 0 o . Ό ^ 4 u υ u rs rό M ri TT 0 u-i vo r- < Table 1 (Continued) NO R 1 1 NO R 2 ^ j|^ )ll () (H) Prep . o . R 1 R 2 s(ale( ,, C) NMR (CDCI,, TMS) δ (ppm) MS (m/e) 13 4-CI-C 6 H 4 C 2 H, 111-112 7.62~7.0()(m, 4H), 3.86(q, 2H), 3.84(d, 2H), 3.55(1 IH), 213(36), 154(100), 140(84) 123(t, 3H) 14 H, n-C,H 7 58-59 7.62-6.98(111, 5H), 3.86(1, 2H), 3.80(d, 2H), 3.45(t, IH), 193(23), 151(44), 106(100), 77(53) 185~l.20(m, 211), 1.20(1,311) 15 4-CH,0-C t H 4 n-C,H 7 40-41 7 l6-6.85(m, 4H), 3.84(s, 3H), 3.7l(d, 2H), 3.65(1.2H), 223(63), 150(40), 136(100), 43(47) 3.46(1, III), l.63~l.46(m, 211), 0.90(1, 3H) 16 H, i-C,H 7 42-43 7.48~6.88(m, 5H).5.05~4.65(nι, IH), 3.t54(d, 211), 193(24), 120(100), 77(52), 43(100) 3.52(1, IH), 1.02(d,6H) 17 2-CH,-C 6 H 4 i-C,H 7 L 7.48~6.98(m, 411), 5.l2~4.64(m, IH), 3.62(d, 2H), 207(47), 134(100), 45(89) 3.34(1. IH), 2.37(s, 3H), l.28(d, 3H), l.00(d, 3H) 18 3-CH,-C 6 H 4 i-C,H 7 51-52 7.49~6.85(m,4ll), 5 I5~4.72(m, IH), 3.72(d, 2H), 207(48), 134(94), 91(72), 45(100) 3.55(t, IH), 2.48(s, 311), 1.08(d, 6H) 19 3-CH,0-C 6 H 4 i-C j ll, L 7.4l~6.6l(m, 4H),5.08~4.84(m, IH), 3.84(s, 3H), 223( 18), 150( 100), 84(26), 45(38) 3.69(d, 2H), 3.57(1, IH), l.08(d, 611) 20 4-CH,0-C 6 H 4 i-C,H 7 96-97 7.32~6.78(m, 4H), 5.25-4.76(m, IH), 3.86(s, 3H), 223(27), 181(47), 150(100), 3.68(d, 211), 3.51(1, 111), I.I (d,6H) 123(79), 107(65), 45(54) 21 3-CF r H 4 i-C,H 7 48-49 7.87~7.2l(m, 4H), 5.18~4.86(m, III), 3.76(d, 2H), 261(26), 188(63), 43(100) "n3 3.51(1, HI), 1.08(d, 6H) 22 4-F-C t H 4 i-C,H 7 52-53 7.2l~7.03(ιπ, 4H), 5.08~4.86(m, IH), 3.6l(d, 211), 211 (20), 138(1 0), 95(33), 43(86) NO NO 3.45(t, IH), l.07(d,6H) © o Table 1 (Continued) vo NO r 4^ ~1 NO o an Prep . No . R' R 1 state (°c) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 23 2-Cl-C,H« i-C.H, 67-68 7.78~7.23(m.4H).5.l6~4.85(m, IH), 3.78(d, 2H), 227(8). 192(69), 154(83), 45(100) 3.500, IH). l.35(d.3H). l.20(d.3H) 24 3-a-cjι, i-C,H 7 62-63 7.58~6.95(πι, 4H), 5.l5~4.85(m. IH). 3.80(d, 2H). 227(27). 1.54(100).43(76) 3.54(1, IH). l.08(d.6H) 25 2-C -F-C.H, i-C,H, 51-52 7.5l~7.l5(m, 3H), 5.l4-4.87(m, IH).3.78(d.2H). 245(19).210(24). 172(28).43(100) 3.48(1. IH). l.32(d.3H). l.l5(d. 3H) 26 3.4-0,-0^, i C.H, 67-68 7.72-6.97(m. 3H). 5.l2~4.84(m, IH). 3.75(d. 2H), 261(36), 188(28).45(100) 3.460. Ill), U6(d.6H) ), 3.82(d, 211). 3.41(t, IH), 3.32(s 3H), 27 3-CH3-C6H« Clb L 7.4r6.84(m, 4H ' 179(61), 120(100), 59(67) 2.37(s. 310 I 7.38~6.87(m, 4H), 3.81(d, 2H), 3.38U, 111), 3. 28 -CH3-C6H4 • Clb 58 31(s, 3H), 2.35(s, 3H) 179(47), 120(100), 59(86) 29 3.82(d, 2H), 3.36(t, 110, 3.33(s, 310, 3,4-(CHj)2-C6H3 Clb 80 7.37~6.84(m, 3H), 193(57), 134(100) 2.25(s, 6H) 30 3-CI-C*H« Clb 66 7.67~7.01(m, 410, 3.84(d, 210, 3.53(t. Ill), 3.36(s, 310 199(58), 140(100). 75(82) 31 3,4-(CH3) 2 -C6H3 i-Cslb 74r6.&5( . 310, 532~4 84(m, 111), 3.70(d, 211), 331(t, HI). 221(61 ), 162(100), 59(48) n H 2.34(s, 610, 1 I8(d, 611) O VO © © Os - 13 - Preparation 32 : P r e p a r a t i o n o f _- 2 - hydroxyacetylpiperidine ( II ) Step 1 : Preparation of M-2-chloroacetylpiperidine( V) The procedure of Step 1 of Preparation 1 was repeated except that 8.5 g of piperidine was used in place of M- methylaniline and that column chromatography using a mixture of n-hexane and ethyl acetate(4:l) as an eluent was conducted in place of recrystallization to obtain 14.8 g(yield 92%) of the title compound as a yellowish brown liquid. H-NMR (CDC1 3 , TMS) 5: 4.08(s, 2H), 3.76-3.18(m, 4H), 1.98-1.21(m, 6H) MS (m/e): 161(M + , 26), 126(100), 69(37), 41(68) Step 2 : Preparation of M-2-acetoxyacetylpiperidine ( IV) The procedure of Step 2 of Preparation 1 was repeated except that 16.1 g(0.1 mol) of the compound obtained in Step 1 was used and that column chromatography was conducted using a 4:1 mixture of n-hexane and ethyl acetate as an eluent to obtain 16.5 g(yield 89%) of the title compound as a liquid. 1 H-NMR (CDCI 3 , TMS) δ: 4.67(s, 2H), 3.68-3.10(m, 4H), 2.12(s, 3H), 1.68-1.38(m, 6H) MS (m/e): 185(M + , 21), 112(51), 69(73), 43(100) Step 3 : Preparation of H-2-hydroxyacetylpiperidine( II The procedure of Step 3 of Preparation 1 was repeated except that 18.5 g of the compound obtained in Step 2 was used and that column chromatography using a 2:1 mixture of n-hexane and ethyl acetate as an eluent was conducted in place of recrystallization to obtain 11.7 g(yield 82%) of the title compound. 1 H-NMR (CDCI 3 , TMS) 6: 4.08(d, 2H), 3.97(t, IH), 3.67- - 14 - 3.02(m, 4H), 1.75-1.15(m, 6H) MS (m/e): 143(M + , 35), 112(86), 69(77), 43(100) Preparations 3.3 to 48 The procedure of Preparation 32 was repeated to obtain compounds of formula (II) having various R and R 2 groups, as in Table 2. The 1 H-NMR and MS analysis data and melting points of these compounds are also shown in Table 2. L in Table 2 represents liquid. Table 2 R 1 so 1 R ^ N γ^t)H 0 (H) Prep. No . R 1 R 2 state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 32 -(CH 2 ),- L 4.08(d, 2H).3.97(1, IH),3.67~3.02(m,4H), 1.75-1. l5(m.6H) 143(35), 112(86).69(77), 43(100) 33 -CH(CH,)(CH 2 ) 4 - L 4.l2(d, 2H), 3.85(1, IH).3.46-2.67(m, 3H). I.94~l.46(m, 6H), 157(37), 126(72).84(100).55(66) l.23(d,3H) 34 -CH(CH 3 CH 2 )(CH 2 ) 4 - L 4.l (d, 2H).4.08(1, IH).3.45-2.64( .3H). I.85~l.38(m, RH), 171(16), 142(38).84(100), 55(48) 0.86(t.3H) 35 -CH(CH,)(CH 2 ) 3 CH(CH,)- L 4.7 l(b, IH).4.l5(d.2H).3.98~3.54(m.2H), l.97-l.46(m,6H), 171(28), 98(97).55(99).41(100) i l.25(d.6H) I 36 (CH 2 ) 2 CH=CHCH 2 - 77-78 5.86~5.69(m.2H).4.l6(d.2H), 4.15(1, IH).3.75~3.64(m.2H). 141 (39).82(57), 67(86), 54(83).41 3.30(1.2H), 2.27~2.05(m, 2H) (100) 37 -(CH 2 ) 1 0(CH 2 ) 1 - 52-53 4.13(d, 2H), 3.80-3.48(m, 8H).3.41(1. IH) 145(75), 100(67).86(55), 42(100) 38 -(CH 2 )C(CΛ)C- 78-79 7.28~7.03(m, 4H), 4.18(d.2H).3.80(1.1 H).3.78~3.54( , 2H). 191(36).132(100), 117(30), 77(49) 2.75(t.2H), l.98(t.2H) 39 (CH 2 ) 6 - L 4.l5(d.2H), 3.84(1. IH).3.78-3.12(m.4H), l.98-l.28(m,8H) 157(11).126(72), 84(100).47(79) 40 C j H, C j H, L 4.05(d, 2H), 3.78(1, IH), 3.48(q, 2H).3.23(q, 2H).1.15(1.6H) 131(25), 100(71).72(100), 44(86) 41 n-C j H, n-C,H 7 L 4.06(d, 2H).3.80(t. III), 3.42(q, 2H), 3.l5(q.2H), 1.85- I.I 5 159(23), 86(29).72(100), 43(94) π Ό H (m, 4H).0.97(1.6H) 42 i-C,H, i-C,H, 63-64 4.08(d, 211), 3.95(1, IH).3.84~3.35(m.2H). I.42(d.611).1.28 159(45), 128(36), 86(94), 43(100) (d, 6H) © 43 CH 2 =CHCII, CII,=CHCH 2 L 6.12-502(tn, 6H), 4.12(d, 2H), 4.01~3.94(m, 411), 3.65(1. IH) 155(36), 124(27), 56(37), 41(100) Table 2 (Continued) vo R 1 1 R I N /N OH 0 (II) Prep . No. R 1 R 2 state(°C) NMR (CDCI,, TMS) δ (ppm) MS (m/e) 44 n-C t H, n- u, 4. l4(d,2H), 3.72(t. IH).3.36(1.4H), l.64-l.l9(m,8H), 187(21), 86(57), 57(100), 44(58) 0.96(1, 6H) 45 i-C.H, i-C,H, L 4.12(d, 2H), 3.74(t, 1 H), 3.24(d, 4H).2.13-1.78(m, 2H), 187(44).144(31), 86(100).57(69) 0.87(d. I2H) 46 C.H, i-C.H, L 4. l4(d,2H).3.81(1, IH), 3.75~3.56(m, IH).3.27(q.2H). 145(11).86(38), 72(97).43(100) l.l8(d.6H), 1.15(1.3H) ■σ. 47 CH, n-C 4 ll, 4.08(d.211), 3.79(1, IH), 3.45(1, 2H), 2.85(s, 3H), 1.78-1.08 145(12), 114(21).57(41), 44(100) I (m,4H),0.98(t,3H) 48 CH, 0,11,01, L 7.25-7.09(m, 5H), 5.45(1.1 H).4.58(s, 2H), 4.38(d.2H), 179(48).120(87).59(100) 2.98(s, 3H) O H vo vo - 17 - Preparation 49 : Preparation of 2 , 2-dif luoro-1- trifluoromethyl-4 '-methoxy styrene( III) Step 1 : Preparation of 2 , 2 , 2-trifluoromethyl-4 ' - methoxyphenylketone(VII) 5.1 g(0.21 g atom) of magnesium was placed in 300 ml of dry diethyl ether and 37.4 g(0.2 mol) of p_-bromoanisole was added dropwise thereto under a nitrogen atmosphere to prepare a Grignard reagent. The Grignard reagent solution was cooled to -78 °C and 28.4 g(0.2 mol) of ethyl trifluoroacetate was added dropwise thereto. The resulting solution was stirred for 30 to 60 minutes, mixed with crushed ice, acidified with concentrated hydrochloric acid and then extracted three times with diethyl ether. The organic layer was dried over magnesium sulfate and the solvent was removed under a reduced pressure to obtain a residue. The residue was distilled at 72 to 73 °C/ 20 mmHg to obtain 35.09 g (yield 86%) of the title compound as a colorless oil. 1 H-NMR (CDC1 3 , TMS) ό: 7.62-6.81 (m, 4H), 3.86(s, 3H) MS (m/e): 204(M + , 56), 135(100), 107(86), 92(66), 77(92) . Step 2 : Preparation of 2 , 2-difluoro-1-trifluoromethyl-4 ' - methoxy styrene(III) 26.2 g(0.1 mol) of triphenylphosphine was dissolved in 250 ml of dry THF and 25.2 g(0.12 mol) of dibromodifluoromethane was added dropwise thereto under a nitrogen atmosphere at a temperature below 10 °C. The resulting solution was stirred for thirty minutes and 10.2 g(0.05 mol) of the compound obtained in Step 1 was added thereto. The resultant solution was refluxed for 12 hours, cooled and distilled under a reduced pressure. The product was redistilled at 72 to 74 °C at 10 mmHg to obtain 9.36 g(yield 78.7%) of the title compound as a colorless liquid. - 18 - 1 H-NMR (CDCI 3 , TMS) δ: 7.48-6.79(m, 4H), 3.79(s, 3H) MS (m/e): 238(M + , 69), 195(14), 145(35), 74(33), 59(100) . Preparations 50 to 65 The procedure of Preparation 49 was repeated to obtain compounds of formulas (VII) and (III) having various R 3 and R 4 groups, as in Tables 3a and 3b, respectively. The H-NMR and MS analysis data and melting points of these compounds are also shown in respective tables. Preparation 66 : Preparation of 2 , 2-dif luoro- 1- pentafluoroethyl styrene(III) The procedure of Preparation 49 was repeated except that bromobenzene and ethyl pentafluoropropionate were used in place of bromoanisole and ethyl trifluoroacetate, respectively, to obtain the title compound. The 1 H-NMR and MS analysis data and melting points of the compounds of formulas (VII) and (III) are also shown in Tables 3a and 3b, respectively. Table 3a °γ RΪ o R 4 Prep. Nos.49-65: R 4 = CF 3 (VII) Prep. No. 66 R 4 = CF2CF3 Prep No. R J 'H-NMR (CDCI,. TMS) δ (ppm) MS (m/e) yield(%) b.p.(mmHg) 49 4-CH j O-C.H,- 7.62-6.8 l(m.4H),3.86(s.3H) 204(56).135(100).107(86).92(66).77 (92) 86 72-73(20) 50 3-CH,C H 4 - 7.52~6.92(m.4H), 2.25(s, 3H) 188(16).135(45).119(96).91(100).65(45) 61 70-71 (20) 51 4-CH Γ C H 4 - 7.42~6.92(m, 4H), 2.25(s.3H) 188(12). II 9(100). 1(96), 65(45) 68 65-66(8) 52 4-C a H,-C 4 H 4 - 746-7.19(m.4H).2.68(q, 2H). I.23(t.3H) 202(40).133(91).105(100).76(64) 62 column 53 3.4-(CH,) 1 -C 4 H J - 7.52~6.69(m.3H).2.23(s, 3H), 2.20(s, 3H) 202(43), 133(98), 69(100) 71 column 54 IMCHλ-CM- 7.3l~7.0l(m.3H),2.25(s,6H) 202(24).133(100), 69(24) 69 column 55 3-CH 1 0-C 4 H < - 7.4 l-6.79(m, 4H).3.79(s.3H) 204(36).135(100).107(56), 77(94) 78 64-65 (33) vD 56 C.H,- 7.52-7. l2(m.5H) 174(21).105(100), 77(82).69(54) 71 64-65 (33) I : 57 4-C 2 H,C C,H- 7.54-«.76(m.4H).4.09(q.2H).1.32(1. H) 218(16).149(88), 121(62).76(100) 69 column 58 3.4-OCH,OC 4 H 4 - 7.92~7.43(m.3H).6.25~6.0l(s, 2H) 218(42), 149(100).65(49) 73 column 59 3-CF,-C,II 4 - 8.60-7.6 l(m.4H) 242(10), 173(68).145(100).76(62) 67 column 60 3-F-C,H 4 - 7.56~6.89(m,4H) 192(25).123(100).95(78).75(31) 54 59-60(30) 61 4-F-C t H 4 - 7.76-6.92(m.4H) 192(16).169(54).123(100), 95(91), 75(76) 59 66-67 (34) 62 3-α-C,H 4 - 8.38~7.45(m, 4H) 208(10).139(93), 111(100).75(64) 70 58-59(10) 63 4-CI- H 4 - 7.51-7.4 l(m.4H) 208(100).173(92).97(54).69(24) 61 83-84 (24) O 64 .l^-Cl j - H,- 8 l2~7.86(m.3H) 242(55).173(100).145(64).109(32) 45 75-76 (4) H 65 C 4 H,S-2-yl- 8.28~7.28(m.311) 180(23). II 1(45).84(100) 76 column vo vo 66 CβHs 7.48~7.02(m, 5H) 224(48), 205(100), 119(75) 68 62~63(22) Table 3b ϊi F »J Prep. Nos- 49-65: R 4 = CF 3 F | Prep. No. 66 : R 4 = CF2CF 3 R 4 (III) Prep No. R> 'H-NMR (CDCI,. TMS) 6 (ppm) MS (m/e) yield(%) b.p.(mmHg) 49 4-CH,OC t H,- 7.48~6.79(m.4H), 3.79(s, 3H) 238(69).195114).145(35), 74(33).59(100) 79 72-74(10) 50 3-CH,- H 4 - 7.46~6.98(m, 4H), 2.43(s, 3H) 222(20).203(70).134(100) 45 column 51 4-CH,-C 4 H 4 - 7.32-7.l8(m.4H),2.45(s.3H) 222(64).203(23), 134(100) 62 column 52 4-C,H J -C 4 H 4 - 7.38-7.25(m, 4H).2.68(q, 2H).1.19(1.3H) 236(20).145(100), 90(54) 62 column 53 SMCHλ-CJήf 7.28~7.02(m.3H), 2.38(s.3H).2.32(β, 3H) 236(18).84(33), 45(100) 78 column 54 1MCH -Cj.t f 7.32-7.l2(m.3H).2.4l(s.6H) 236(29).217(68). I4B( 100).45(92) 98 column tvj 55 3- i 1 0-C„H 4 - 7.48~6.87(m, 4H).3.8 l(s, 311) 238(42), 207(45), 188(37)..139(100).69(94) 54 75(10) o 56 C.H,- 7.59-7.3 l(m,5H) 208(48).84(83).43(100) 67 column 57 4-C 2 H J OC l H 4 - 7.51~6.85(m,4H).4.l2(q, 2H), 1.29(t, 3H) 252(47).233(100), .84(64) 73 column 58 3,4-OCH,O 4 H 4 - 7.0l~6.79(m.3H).6.0l(s.2H) 252(46), 233(63), 164(82), 69(100) 72 column 59 3-CF 3 < H 4 - 7.82-7. l8(m.4H) 276(52), 257(92).188(100) 52 column 60 3-F-C 4 H 4 - 7.53~6.96(m.4H) 226(52), 207(25), 84(100) 54 column 61 4-F-C 4 H 4 - 7.52~6.83(m, 4H) 226(20).84(100) 63 column 62 3-Cl-C.H 4 - 7.54~7.23(m, 411) 242(26), 223(72).188(49).69(100) 63 column 63 *0 4-CI-C 4 H 4 - 7.56-7.2 l(m,4H) 242(35).207(25), 174(70).139(100), 60(79) 45 58(10) O 64 H 3.S-α,-C^l r 7.57-7. l9(m.3H) 276(100).241(45) 84 85(10) 65 C 4 H,S-2-yl- 7.67~6.92(m, 3H) 214(42), 195(92).126(100), 47(86) 63 column vo o 66 CβHs 7.57~6.-®(m, 5H) 246(67), 227(57), 127(100), 119(35) 48 138~139(737) ≥ o - 2 1 - Example 1 : Preparation of N-methyl- ( 2 ' -fluoro-1 ' - trif luoromethylstyryl-2 ' -oxy ) acetanilide ( Compound 1 ) 330 mg(2 mmol) of N-methyl-2-hydroxyacetanilide obtained in Preparation 1 was added to 10 ml of acetone and 0.22 ml of 10M sodium hydroxide solution (2.2 mmol) was added thereto. The resulting solution was stirred for 30 minutes and 416 mg(2 mmol) of 2 , 2-difluoro-1-trifluoromethyl styrene obtained in Preparation 56 was added slowly thereto. The resultant solution was stirred for 1 to 2 hours. Acetone was removed under a reduced pressure and the resulting solution was mixed with water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and the solvent was removed under a reduced pressure. The residue was subjected to silica gel column chromatography using a mixture of n-hexane and ethyl acetate (9:1) as an eluent to obtain 655 mg(yield 92.8%) of the title compound having two isomers as a colorless liquid. H-NMR (CDC1 3 , TMS) δ: 7.52-6.91 (m, 10H), 4.49 (E isomer ) 4.30 ( Z isomer ) ( s , 2H), 3.30(s, 3H) MS (m/e): 353(M + , 12), 177(42), 120(100), 91(72), 77(96) 19 F-NMR ( CDC1 3 , CFC1 3 ) δ : - 57 . 36 ( 2. isomer ) -57 . 95 ( E isomer) (d, 3F), -83.40(E isomer) -84.99(2 isomer) (q, IF) Example 2 : Preparation of (E ) -M-methyl- ( 2 ' -fluoro-1 ' - trif luoromethylstyryl-2 ' -oxy) acetanilide (Compound 2) The compound obtained in Example 1 was subjected to column chromatography using a mixture of n-hexane and ethyl acetate(9:l) as an eluent to isolate a pure form of the E. isomer as a colorless solid. £ isomer 1 H-NMR (CDCI 3 , TMS) δ: 7.54-6.90(m, 10H), 4.49(s, 2H), 3.31(s, 3H) - 22 - MS (m/e): 353(M + , 43), 177(48), 120(100), 91(68), 77(82) 9 F-NMR (CDC1 3 , CFCI 3 ) δ: -57.95(d, 3F), -83.40(q, IF) m.p.: 91-92 °C Example 3 : Preparation of ( ) -M-methyl- (2 ' -fluoro-1 '- trif luoromethylstyryl-2 ' -oxy) acetanilide (Compound 3) The compound obtained in Example 1 was subjected to column chromatography using a mixture of n-hexane and ethyl acetate(9:l) as an eluent to isolate a pure form of the Z. isomer as a colorless oil. Z. isomer 1 H-NMR (CDCI 3 , TMS) δ: 7.51-7. ll(m, 10H), 4.30(s, 2H), 3.30(s, 3H) MS (m/e): 353(M + , 57), 177(40), 120(100), 91(70), 77(97) 19 F-NMR (CDCI 3 , CFCI 3 ) δ: -57.36(d, 3F), -84.99(q, IF) Examples 4 to 220 Using each of the alcoholic compounds obtained in Preparations 1 to 31 and each of the fluorovinyl compounds obtained in Preparations 49 to 66, the procedure of Example 1 was repeated to obtain 217 compounds (Compounds 4 to 220) of formula (I) of the present invention having various R 1 , R 2 , R 3 and R 4 groups listed in Table 4. The 1 H-NMR and MS data and melting points of these compounds are also shown in Table 4. L in Table 4 represents liquid. - 23 - s s s w, •c c- δ σv w. ac s X ar © & c 5f " * ^ s s ■ v £ ■ v M" άe © o 5 8 5 ae w- — — β ~v -. — CM W-. "- ■ VO J- 1 CM J— ' l"» — 5r vo — • c " _ t— <— r— — c- — S t 5 C CM r» . c» . r- CM -^ — ~Z r~ -£ \r . . x ~ ; w. ~ w. • — 4 » - as — cs ^ αe o O ^r i^ c M O ^ c vo cM os v σv vΛ wo r, 4--- O - CO ^r * ^j, » «™ ^ •• .^. .™ ^« (— o 4O wo — wo — w. — vo — vo — sc — oc — ac — ac oc » r, » n ft n » n » n eι i"i cι f ι » r 4. i4v. - ?! X I ϊ r! r- c- ac IL υ — c co f -i » ~ c_= _ ~ _ ~ .—^ _ -: rs δ - δT fvj «" " i f fj fj fϊ ivl f? CO -J I CM ( a 6? r- ac 5C 5? ^ β\ .ac 1 - σ>. — — — σv CD ! ^ <- oo r C CM S vo oe ^ - (<- 3C »ι fO vo r- vO ; vo - 1— r÷ r~ • vo »• v5 „- 1 1 — v tr.. i ^r ■ • v rr^~ ^ —— oo aoee —— «γ-> r- - — - - - -- - -- θ r- o r- r» r- r» s r- CM Cv _: _J _ι -: _j _: _: — Ov X sj u * 0 υ * ϋ° υ * X — — -5 0 u υ tJ af x — X ^ u υ wo ^r u C 0 υ υ ϋ υ ϋ O C x x x x S? 5 u * d" ϋ * <o r- Table 4 (Continued) vo r VO Rϊ o R< R< = CFs (I) Cornp . No . R' R' state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) I I o Λ CH, 4-C,H,O C t H 4 L 7.42-6.80(m.9H).4.48(E) 4.30(Z)(s, 2H), 3.98(q, 2H), 397(49).249(30). 148(100), 3.32(s. 3H). 1.39(1. 311) 120(81) 12 C,H, CH, 3.4-OCH,O C # H, L 7.68~6.82(m. 811). 5.92(s. 2H). 4.49(E) 4.30(Z)(s. 2H). 397(35). 148(100). 120(70). 3.33(s, 311) 77(43) 13 C.H, CH, 3 CF,-C,H 4 L 7.68-6.91 (m. 9H). AA (E) 4.31 (Z)($. 2H). 3.31 (s. 3H) 421(35). 402(19). 148(100). 120(99). 91(54) 14 C.H, CH, 3-F-C t H 4 L 7.62~6.99(m. 9H).4.49(E) 4.3 l(Z)(s. 2H). 3.32(s. 3H) 371(40). 148(100), 120(91). 96(40. 77(37) IS C.H, CH, 4-F-C t H L 7.68~6.98(m. 911).4.48(E) 4.30(Z)(s, 211). 3.33(s. 3H) 371(30). 148(100). 120(78). 77(42) 16 C.H, CH, 3-CI-C I, L 7.72~7.0l(m, 911). 4.49(E) 4.30(Z)(s. 211). 3.34(s. 3H) 387(62), 148( 100). 120(45). 77(47) 17 H, CH, 4 CI-C 4 H 4 L 7.65~6.98(m. 911). 4.48(E) 4.3 l(Z)(s. 2H), 3.35(s, 311) 387(59). 148( 100). 120(95). 91(46) 18 C I, CH, 3,5-CI,-C k H, L 7.52~7.09(m, 811). 4.49(E) 4.32(Z)(s. 211), 3.3 l(s, 311) 421(25). 148(100), 120(84), 77(48) 19 C I, CH, C 4 H,S-2-yl L 7.62~6.95(m. 811). 4.49(E) 4.32(Z)(s. 211). 3.32(s. 311) 359( 10), 148( 100). 120(58). * 77( 15) O H 20 4-CH,O C,H 4 CH, C.H, L 7.52-6 87(m, 911), 4.49(E) 4 3 l(Z)(s, 211). 3.85(s. 311). 383( 12). 178( 100). 144(81 ). 3.32(s. 311) 121(48) vo o Table 4 (Continued) VO O R> F VO w N γ^o - RJ O R R = CFs (1) Comp No. R' R' R» state( 0 C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) " 4-CH,OC.k 4 CH, 3CH,- ;H 4 L 7.43-6.76(m.811), 4.48(E) 4.29(Z)(s.2H), 3.85(», 3H), 397(47).178(100).147(40) 3.3I(».3H).2.35(»,3H) 22 4-CH,OC,H 4 CH, 4CH,-C H 4 1. 7.49~6.79(m, 8H).4.48(E) 4.28(2)(s.211), 3.84(β.311), 397(100).372(33).178(98). 3.3l(s.3H), 2.35($.3H) 150(53) 23 4-CH,0-C.H 4 CH, IMCH -C 1-82 7.55-6.79<m, 711).4.49(β-) 429(Z)(s, 211), 3.85(x, 311), 411(40), 178(100), 147(69) 3.33(ϊ,3H).2.3l(s.6H) 24 4-CH,OC,H 4 CH, 3.5-(CH,VC,H, 7.62-6.78(m. m),4.49(E) 4.VXZK*.2H), 386(s.3H). 411(51).178(100).147(47), 3.32(s.311).2.30(s.611) 121(36) en 25 4-CH,0-C.H 4 CH, 4CH,OC.H 4 7.56~6.72(m.811), 4.49(E) 4.32(Z)(s, 2H).3.87(*.3H), 413(24).178(100).147(37) 3.85(s.311).3.30(s.311) 26 4CH,OC t H 4 CH, 3.4 OCH,0-C,H, L 7.59~6.52(nι.711).5.94(.ι, 211).4.49(E) 4.3I(Z)(*.211), 427(41).178(100).147(25), 386(s.311).3.3l(t.3H) 121(24) 27 4-CH,O .H 4 CH, 3-CI-C.II 4 L 7.56~6.85(m, 811).4.49(E) 4.30(Z)(s.211).3.86(s.3H). 417(18), 178(100), 147(46), 3.34(5.311) 121(41) 28 4-CH,OC.H 4 CH, 4CI-C.H 4 82-8.1 749-6.87(m, 8H).4.48(E) 4.1(KZ)(s.211).3.85(5.311), 417(20), 178(100), 147(88), 3.42(s.3H) 121(58) 29 4-CH,OC.H 4 CH, i.s-ci-c.π, L 7.7 l~6.98(ιn, 711), 4.49( £T) 4.3 l(Z)(s.211).3.85(s.3H). 451(35).178(100), 147(82). .1.32(5.3H) 121(70) O H 30 4-F-C,ll 4 CH, C.H, 1. 7.54~7.03(m, 911), 449(E) 43l(.Z)(s.2H).3.33(s.311) 371(41).166(100), 138(84). 109(78) vo vo o © Ov Table 4 ( Continued ) o ^ rVN)' -R 3 O R 4 R 4 = CF 3 (I) Comp . No . R' state( 0 C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 31 4-F-C.H. CH, 3-CH,-C,H 4 L 7.32-7.02(m. 811), 4.49(E) 4.30(2)(s.211). 3.30(s. 3H). 385(43), 166(100). 138(82). 2.35(s. 3H) 109(79), 95(30) 32 4-F-C,H 4 CH, 4-CH,-C,H L 7.36-7.00(m. 8H).4.49(E) 4.3I(2)(».2H).3.32(s.3H). 385(21), 166(100). 138(94). 2.33(s, 311) 109(80) 33 4-F-C.H 4 CH, 3.5 (CH,) r C.H, L 7.30~6.93(m. 711).4.49(E) 4.30(Z)(s. 211), 3.31 («. 3H). 399(50). 166( 100), 138(76), 2.32(s. 6H) 109(69) 34 4-F-C,H 4 CH, 3-CH,O C.H 4 L 7.3 l~6.83(m. 8H).4.48(E) 4.30(Z)(s. 2H). 3.86(s. 3H), 401(57), 166(100), 138(67), 3.32(s, 311) 109(45) •NJ 35 4-F-C.H 4 CH, 4 CH,O C.H 4 L 7.35-6.78(m. 811), 4.49(E) 4.30(.Z)(s, 2H), 3.84(s, 3H). 401(42). 166(100). 138(52). <Jv 3.33(s, 3H) 109(44) 36 4 F-C,H 4 CH, 3 F-C.H 7.39-6.94(m, 811), 4.48(E) 4.3 l(^(s. 2H), 3.3 l(s. 3H) 389( 1 ). 166(89). 138( 100). 109(80).95(30) 37 4-F-C.H 4 CH, 4-F-C.H, L 7.46-6.94(m. 8H), 4 49(E) 4.3 l(2)(.s. 211). 3.32(s. 311) 389(56). 166( 100). 138(91). 109(76). 95(29) 38 4-F-C.H. CH, 3-CI-C.H 4 L 7.48-7.06(m. 8H).4.49(E) 4.32(Z)(s. 211). 3.33(s. .Ill) 405(26), 166(60), 138(42). 109(39).43( 100) 39 4 F-C.H 4 CH, 4-CI-C.H 4 L 7.45-7.05(m. 811). 4.48(E) 4.30(Z)(s, 211). 3.32(s. 311) 405(41), 166(100). 138(84). 109(73). 95(35) O 40 4-F-C,H 4 CH, 3.5-01,-0.11, L 7.34~7.08(m. 711), 4.49(E) 4.3l(.Z)(s. 211). 3.30(s. 311) 439(46), 166( 100). 138(89). H 109(90), 95(38) J o o o o Table 4 (Continued) r ~ *j o ^ R 4 = CF 3 (I) Comp . _No . R' R' R' state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 41 4-CI-C.H, CH, 3 3..55--00,,--00.,1111,, 13 366--137 7.50-7.05(m. 7H).4.48(E) 4.30(Z)(s.2H).3.3l(s.311) 455(31). 182(56). 147(100). 118(35). 77(24) 42 2,4 F a C,H, CH, 3 CI-C,H 4 L 7.45-6.85(m. 711).4.49(E) 4.30(Z)(s. 211), 3.32(s, 3H) 423(21), 184(34). 156(24), 127(100) 43 4>.4-α,-C.H, CH, 4 F C,H 4 L 7.79-6 87(m. 711), 4.48(E) 4.3 l(Z)(s, 2H), 3.33(s, 3H) 439(34). 216(57). 181(100). 145(50) 44 vC.II, C,H, C.H, L 7.65-7.09(m. 1011).4.41(E) 4 28(2)(s, 211).3.75(q. 2H). 367(12), 162(100). 134(79). 1.13(1. 311) 106(57).91(55) t 45 C.H, C,H, 3-CH,-C,H L 7.49~7.0l(m. 911).4.42(E) 4.29(Z)(s. 211). 3.76(q. 2H), 381(100).363(10). 162(56), -4 2.39(s, 3H). 1.14(1. 3H) 134(64) 46 C.H, C,ll, 3 CH,O C.H 4 L 7.62~6.8l(m, 911).4.43(E) 4.28(Z)(s, 2H). 3.85(s. 3H), 397(29), 378(16). 162(99), 3.74(q, 211). 1.14(1, 3H) 134(100), 106(78) 47 C.H, c.ιι, 4-0,11,0 0,11, L 7.42~6.75(m, 9H). 4.42(E) 4.28(.Z)(s. 211). 3.94(q. 2H). 411(25). 221(54). 162(100), 3 72(q.2H), 1.34(1.3H), 1.13(1.311) 134(72) 48 C.H, Call, 3 CF,-C.H 4 L 7 82-7.02(m. 911).4.42(E) 4.29(Z)(s.211), 3.74(q. 2H), 435(16), 162(100). 134(89). 1.14(1, 311) 106(46) 49 C.H, C.H, 3-F-C.H, L 7.49-6 90(m.911).4 42(E) 4 28(Z)(s, 211). 3.75(q, 211). 385(30), 162(100). 134(71). I 11(1.3H) 106(43) S 50 C.H| C,H, 4 F-C„H 4 L 7 62-692(m. 911).4 41(E) 4 29(-Z)(s, 211). 3.76(q. 2H). 385(39). 162(100). 133(80). I 14(1. 311) 91(5.1) o vo δ o Table 4 ( Continued ) ϊ ~iJ vo R*' 0 h* R 4 = CFa (I) Comp . No . R' R' R 1 .state( 0 C) NMR (CDCI,. TMS) δ (ppm) MS (m/c) 51 C.II, C,H, 4-CI-C,H 4 7 57-6 98(m. 911).4 42(E) 4 29(Z)(s. 211). 3.76(q. 2H). 401(40). 162( 100). 134(56) 1 14(1, 311) 52 C,H, C,H, C 4 H,S-2-yl L 7 68-6 91(m. 811), 4 42(E) 4 28(Z)(s, 211), 3.75(q, 211). 373(31). 162( 100). 134(32) 1 16(1. 3H) 53 4-CH,-C,H 4 C,H, C.H, L 749-694(m. 911).4.43(E) 4 28(Z)(s.2H). 3.74(q. 2H). 381(55), 176(100), 105(44) 2 39(5, 311). 1 13(1, 3H) 54 4-CH,-C,H„ C,H, 4-F-C.H. L 7 63-6 89(m. 8H).4 42(E) 4 29(Z)(s, 2H). 3.74(q. 2H). 399(55). 176(100), 148(55) 2 38(s. 311). 1 12(1. 311) t 55 4-CH,O C,H 4 C,H, C.H, L 7.49-6 85(m, 911).4.41(E) 4 27(Z)(s, 211). 3.8 l(s. 3H). 397(23). 378(12). 193( 100), CD 3 72(q. 2H), 1.13(1. 311) 165(36) 56 4-CH,0-C,H 4 C,H, 4-F-C.H 4 L 7 48-6 84(m, 811), 4 42(E) 4 28(Z)(s. 2H). 3 82(s, 3H). 415( 14). 192( 100). 1-64(43). 3 75(q, 2H). 1.12(1.311) 121(75) 57 3-CF,-C,ll 4 C,H, C,H, 52-53 7 81-7 23(m. 911).4.43(E) 4.29(Z)(s. 211). 3.75(q. 211), 435(26). 221( 100). 174(61). 1 11(1, 311) 159(69) 58 3-CF,-C,H 4 C,H, 4 CH,-C,H 4 48-49 7 86-7 02(m, 811). 4 41(E) 4 28(Z)(s. 211). 3.72(q, 211), 449( 10). 230( 100). 202(36). 2 38(s. 3H). 1.12(1. 311) 174(27) 59 3-CF,-C,H 4 C,H, 4 F C,H 4 L 7 89-6 85(m, 8H). 4 41(E) 4 29(Z)(s. 211). 3 73(q. 211). 453(26). 231( 100). 201(61) 1 14(1. 311) n 60 2-CI-C,H C,H, C.H, L 7 60-7 12(m. 911). 4 40( E) 4 28(Z)(s, 211).4 02(m. 111). 401(72). 182(15). 196(100). H 1 48(m, I I I), 1 12(1, 311) 168(44). 146(35) 8o vo δ © Table 4 (Continued) VO VO U' F ≥ --1; VO R>" ° R 4 R 4 = CFa (I) Comp No. R' R' R' state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 6i 2-ci-c,ii 4 C,H, 4-CH,-C,H 4 L 762~7.02(m, 8H).4.40(E) 428(Z)(s, 211), 4.06(m, IH), 415(26), 196(100), 118(35) 349(m, IH).239(5.311).1.14(1.3)1) 62 3-CIC,H 4 C,H, C.H, L 749-694(m, 9H), 441(E) 428(Z)(s.211).3.73(q, 211). 401(14).196(100).168(24), 113(1.311) 146(27) 63 4-CI-C,H 4 0,11, C.H, L 750-690(m.911), 440(E) 4.28(Z)(s.2H).3.74(q, 2H). 401(10).196(100).146(37), 114(1.311) 118(18) 64 4CIC,H 4 0,11, 4-CH,-C.H 4 70-71 762-695(m, 8H).440(E) 429(Z)(i.211).3.76(q, 211), 415(12).196(81), 161(100). 239(5.311), 114(1.311) 118(27) 65 C,H, n-C,H, C.H, L 750-702(m. I0H).4.40(E) 42S(Z)(s.2H).365(1.2H). 381(11).176(100).134(84), vO 168-14l(m, 2H),09I(I. Ill) 106(93).77(62) 66 C,H, n-C,H, 4CH,-C,H 4 L 7.62-697(m.9H).4.40(E) 4.26(.Z)(s.2H).3.64(1.211). 395(20).377(13), 176(100). 2.32(5.311). l.67-!.42(m, 211).0.91(1.311) 67 4011,00,11, n-C,H, C.H, L 7.53-686(m.911).4.40(E) 4.25(Z)(s.211).3.8 l(s.3H), 411(24).206(100).178(35). 365(1, 211), 165-1.4 l(m.211), 091(1, 311) 164(48), 136(42) 68 4-CH,OC,H 4 n-C,H, 4-CH,C.H 4 L 762-679(m.811).4.39(E) 4.25(Z)(s, 2H).3.83(s.3H). 425(29).406(14), 203(100) 365(1.211).2.32(s.311). I.68-I.42(m.211).0.92(1.311) 69 C,ll, 1-0,11, C.II, 54-55 7.50-7.0l(m.1011).509-487(m. Hi), 4.10(E) 4 \4{Z) 381(12).176(59).134(100). (5,211). l.08(d.6H) 106(97).77(89) 70 C,H, i-C,H, 3CII,C,H 4 762-682(m.911).510-489(ιn, IH).429(15) 4 I6(Z) 195(19).176(34), 134(100), n (s, 211), 239(s.3H), I09(d,61l) 106(69) o o Table 4 (Continued) VO O ≥ 1 « F VO ° R 4 R 4 = CFa (I) Comp . No . R' R' R' state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 71 C,H, i-C,H, 4-CH,-C,H 4 67-68 7.62-6.97(m.911).5.28-4.86(m. III).4.29(E) 4.1 * 5(2) 395(65), 376(49).176(100). (s.211).2.46(s.311). I.09(d, 611) 106(76) 72 C.H, l-C,H, 3.5 (CH,VC,H, L 7.64-6.85(m.811).5.20-4.88(m. Ill), 4.30(E) 4.16(Z) 409(56), 134(100).106(87). (5,2)1), 2.38(5.611). I.09(d.611) 77(52) 73 C,H, i-C,H, 3CH,OC,H 4 L 7.5 l-6.79(m.9H).5.19~4.84(m.1 H).4.28(E) 4.1 (Z) 411(30).176(39).134(100). (s, 211).3.80(s.311). l.08(d,6H) 106(50) 74 C,H, IC,H, 4CH,OC,H 4 48-49 7.7l~6.95(m.9H).5.2l~4.85(m, IH), 4.29(E) 4.15(Z) 411(33), 176(57).134(100), (s, 2H).3.8l(s, 3H), l.09(d.6H) 106(74) 75 C,H, IC,H, 4-C,H,OC,H 4 L 7.48-6.79(m.9H).5IO-4.84(m. IH), 4.2i(E) 4Λ6(Z 425(70), 176(63), 134(100), o (s, 211), 4.40(q.211), 1.38(1, 311), 109(d.611) 106(69), 84(55) 76 C.H, i-C,H, 3.4-OCH,OC.H, L 7.59-6.75(m.8H).5.96(s.211).5.1 l~4.86(m, IH). 425(15), 219(30).134(100). 4.29(E) 4. l6(Z)(s.2H). l.08(d.6H) 106(60) 77 C.H, l-C,H, 3-F-C.H 4 7.50-6.9l(m.911), 5IO~4.82(m.lH), 4.29(E) 4.I4(Z) 399(40).134(100), 106(70) (5.2H). l.09(d,6H) 78 C.H, i-C,H, 4-F-C.H, L 7.54~6.89(m.911), 5.09-4.84(m, III), 4.28(-E) .I5(^ 399(35).176(45), 134(100), (S.2II). l.08(d,6H) 106(83) 79 C.H, " C.H, 3CI-C.H, L 7.69-6.94(m, 911).5.11-488(m. III), 4.29(E) 4 I5(Z) 415(45).176(31).134(100). (S.2II). I.08(d, 611) 106(65) 0 80 CJU J-c.il, 4-CI-C.H. 72-73 7.87-687(m.9H).5.21-487(m. III).4.28(E) 4.14(Z) 415(25).176(28).114(100). O H (s,2ll), I09(d.6ll) 106(73).78(34) 1 vo vo © © Table 4 (Continued) vo ^1 vo 81 C.H, I C,H, C C 44 HH,,SS--22--yyll 6 633--614 7.50-6.94(m.811), 5 l8-4.8l(m. IH).4.29(E) 4.I6(Z) 387(22). 176(31). 134(100), (S. 2H). l.08(d.6H) 106(85). 77(41).43(46) 82 2-CH,-C,H 4 l-C,H, C,H, L 7.61 -6.97(m.911).5.00~4.78(m, I H), 4.28(Q 4M(Z) 395(46), 148(100), 120(47), (dd.2H), 2.32(s, 311). I.27(d.3H). I.02(d.3H) 45(23) 83 2-CH,-C,H 4 1-C.II, 4-CH,-C,H 4 L 7.48-6.95(m. 811).4.95~4.75(m. 1 H).4.29(E) 4.15(Z) 409(9). 190(34). 148(100), (dd. 2H). 2.33(5, 311). 2.31(5, 311). I.30(d, 3)1). 120(80). 1 18(30). 91(30). l.00(d, 3H) 45(42) I 84 2-CH,-C,H 4 l-C,H, 3,4-(CH,),-C,H, L 7 42-7.00(m. 7H). 4.96-4.76(m, I H), 4.28(E) 4, 15(Z) 423(15). 148(100). 120(49). ) (dd, 211), 2.33(s, 311), 2.30(s, 611), l.30(d. 311). 45(22) I .02(d, 3ll) 85 2-CH,-C,H 4 I C,H, 3,5 (CH,),-C,H, L 7.40-6.85(m.711).4.95-4.76(m. I H).4.28(E) 4.16(Z) 423(20), 148(100). 120(45). (dd.211). 2.33(5. 311), 2.31(5, 611), 1.31 (d, 311), 45(24) I 0l(d, 3ll) 86 2-CH,-C,H, l-C,H, 3-CH,0-C,H 4 L 7.46~6.75(m.811), 4.90-4.72(m. I II), 4.28(.E) 4.16(Z) 425(8), 148(100). 120(82). (dd, 211), 3.82(5, 311). 2.32(5, 311). I.28(d, 311), 45(39) 0.98(d. 311) 87 2-CH,-C,H 4 i-C,H, 4 CH,O C,H 4 L 7.40-6.80(ιn.811). 4.9l-4.75(m. IH). 4.28(E) 4.15(Z) 425(8). 148( 100). 120(63). (dd, 211). 3.8 l(s. 311), 2.31(5. 111). I .29(d. 311), 45(25) O 0.99(d, 311) H 88 2-Cli 1 -C,ll 4 1 0,11, 3-ρ-gι, L 7.38-6 87(m. 811). 4.91-4 72(m, I II). 4.28(^ 4 I6(Z) 413(54). 148( 100). 120(68). (dd. 211). 2.3l(s. 311). I .29(d. 311).0.98(d. 311) 45(39) I vo vo δ © Table ( Continued ) r vo „R J R^ N ^O' υ R 4 = CF 3 (I) Comp . No . R' R' state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 89 ΣΪHT H; tCJΪΪ, 4-F-C.H L ~ 7.5 l-6.95(m. 811), 4.97~4.78(m. IH).4.2 (E) 4.15(Z) 413(22). 190(89), 148(100), (dd, 211). 2.30(s. 311), l.2S(d, 311). I.0l(d, 3H) 120(94). 91(73) 90 2 CH, C,H 4 I C,!!, 3-O C.H 4 L 7.54-7.00(m.8H).4.96~4.74(m. IH).4.27(,E) 4. I6(.Z) 429(16). 148(100). 120(51), (dd, 2H).2.28(s, 311), l.30(d, 311), l.0l(d, 3H) 45(23) 91 2-CH,-C,H 4 l-C,H, 4-CI-C,H 4 L 7.50-7.00(m, 811).4.95~4.76(m. IH).4.28(^4.15(2) 429(30), 148(100), 120(52). (dd. 2H).2.29(s. 3H). I.28(d. 3H). l.00(d.3H) 84(32).45(36) 92 2-CH,-C il 4 i-C,H, 3.5-0,-0,11, L 7.52-7.0O(m.7H).4.95~4.75(m. I H), 4.27(E) 4.15(Z) 463(16). 148(100). 120(73). (dd, 211), 2.28(s, 311), l .30(d. 3H), l.0l(d.311) 45(45) » 93 3-CH,-C H 4 i-C,H, C,H, 64-65 7.45~6.80(m.9H).5.02-4.79(m. I H).4.30(E) 4.12(Z) 395(14). 190(56). 148( 100). NJ (s. 211). 2.35(s. 3H). 1.08(d. 611) 120(95), 91(35) 94 3-CH,-C,H 4 i-C,H, 3-CH,-C,H 4 L 7.32-6.79(m, 8H). 5.03-4.80(m, I H), 4.30(E) 4.15(Z) 409( 1 1), 190(28), 148(100). (s. 211). 2.34(s. 311). 2.30(5. 3H). I.09(d. 611) I20(5 I), 84(39) 95 3-CH,-C,H 4 l-C,H, 4-CH,-C,H 4 76-77 7.32-6 80(m. 811). 5.04-4.83(m, I H).4.28(E) 4.14(2) 409(36), I9Q(60), 148( 100), (s, 211). 2.38(s. 3H). 2.3 l(s. 311). I .05(d, 611) 120(54) 96 3-CH,-C.H 4 i C,H, 4 -C,H,-C,II 4 66-67 7.40-6 8 l(m. 811), 5.04-4.84(m. I H).4.30(^ 4.16(2) 423(41). 190(47). 148(100). (s. 211). 2 65(q, 2H). 2.38(s. 3H). 1.26(1, 311), 120(60). 91(21) l .09(d.6H) 97 3-CH,-C.H 4 i-C,H, 3,4 (CH,), C.H, L 7.48-6 8 l(m.711). 5.03-4.85(m. Ill), 4.31(E) 4. I7(Z) 423(56). 190(39). 148( 100). o (s, 211). 2.39(s, 311), 2.25(s.611). I .08(d. 611) i 20(52). 91(20) H 98 3-Cli,-C,H 4 i-C j H, 3,5-(CH,), C.H, 60-61 7.38-680(m, 711). 5.05-4.85(m, IH).4.29(^ 4.15(2) 423(57). 190(69), 148(100), o (s. 211). 2.35(s. 311). 2.29(s.611). I.07(d. 611) 120(63).91(24) vo © © Ov Table 4 ( Continued ) o 5: ,R J R^ rN^O' υ R 4 R 4 = CFa (I) Comp . No . R * R 1 state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 99 3-CH,-C,H 4 i-C,H, 3-CH,0-C,H 4 46-47 7.4 l-6,82(m. 811), 5.06-4.86(m. Ill), 4.30(E) 4.16(2) 425(58). 190(37). 148( 100). (5, 211), 3.80(s, 311). 2.35(s, 311). I . IO(d, 611) 120(53) 100 3-CH,-C,H l-C,H, 4-CH,0-C,H 4 68-69 7.37-6.79(m. 8H). 5.0l-4.80(m, III). 4.30(E) 4Λ5(Z) 425(31). 190(71). 148( 100), (s, 211), 3.82(5. 311). 2.34(5. 311). I.07(d, 611) 120(79), 91(30) 101 3 011,-0,11, l-C,H, 3-F-C,H 4 42-43 7.35-6 ή I (m. 811). 5.01 ~4.78(m. I H). 4.30(E) 4.14(2) 413(57). 190(37). I4B(I00), (s. 211). 2.35(s. 311). 1.09(d. 611) 120(54) 102 3-CH,-C,H 4 l-C,H, 4-F-C.H, L 7.50-6.85(m. 811). 5.04-4.85(m. I II). 4.30(E) 4.16(2) 413(51 ), 148(100). 120(90) (s, 211), 2.39(s. 311). I.09(d, 611) 103 3 CH,-C,H 4 I C,H, 3 CI-C,H 4 L 7.48-6.7B(m. 811). 5.04-4.85(m. \il), 4.3\(E) 4Λ4(Z) 429(25), 148(100). 120(8.1) to (s, 211), 2.38(s, 311), 1.08(d, 611) 104 3-011,-0,11, l-C,H, 4 CI C,H 4 56-57 7.40~6.62(m, 811), 5.02~4.B5(m. I II). 4.30(E) 4.15(2) 429(55). 190(23), 148(100), (5. 211), 2.38(s. 311). 1.08(d, 611) 120(53) 105 3-011,-0,11, i-C,H, 3.5 0,-0.11, 58-59 7.35-6.80(m, 711). 5.00~4.80(m, III), 4.31(^ 4.17(2) 463(51). 148(100). 120(37) (s. 211). 2.35(s. 311). I .07(d. 6ll) 106 3 CII,O C,H, i-C.II, C.H, 80-81 7.50~6.58(m, 911), 5.08~4.85(m, I II). 4.29(^ 4.14(2) 41 1(28). 208( 100). 165(82), (S.2II). 3.82(s. 3H). l.09(d.6H) 137(36) 107 3-CH,0-C,ll, i-C,H, 4 Cll j -C.ll, 9.1-94 7.52-6.53(m. 811). 5.23-4.7B(m. I II). 4.30(E) 4.15(Z) 425(38). 375( 100), 1 18(78) -a (s, 211), 3.82(s. 311). 2.4 l (s. 311). I . l2(d, 611) O H 108 3 CH,O C,H 4 1-0,11, 4 F C.H, 50-51 7.45-6.55(111. 811). 502~4.85(m. Ill), 4.31(E) 4.16(.2) 429(52). 206(82). 164( 100), (s. 211), 3.80(5, 311), I 09(d, 611) 136(86), 45(24) vo vo © δ Table 4 (Continued) VO VO Dl F ≥: vo R» ° R 4 R 4 = CFa (I) Comp No. R' R " R' state(°C) NMR (CDCI,, TMS) δ (ppm) MS (m/e) J09 3-CII,0-C,H 4 i-C,H, 3CI-C,H L 7.5 l-6.76(m, 811).5.02~4.82(m. III).4.30(E) 4.14(2) 445(50).206(50).164(100). (s.211), 3.82(5.311). I.02(d.6ll) 136(68).45(54) no 3-CH,OC,H 4 i-C,H, 4-CI-C,H 4 60-61 7.45-6.58(m.8H).5.02-^.85(m. IH), 4.29(^4.14(2) 445(24).206(66).164(100), (s.211), 3.8l(s.311). I.IO(d.611) 136(92).45(37) III 3-CH,0-C,H 4 l-C,H, 3.5-σ,-C,H, L 7.41 -6.61 ( .7H).5.00~4.84(m. IH).4.30(E) .15(2) 479(5I),206(54).164(100). (5.211).3.81(5.311). I.09(d.611) 137(74).45(26) 112 4-CH,OC,H 4 l-C,H, C,H, L 7.49-6.8 l(m.911).5.04-4.82(m, 1 H).4.29(E) 4.13(2) 411(56).206(68), 164(100). (5.211).3.8l(s.311). I.04(d.611) 136(52).121(74) 113 4-CH,0-C,H 4 l-C.H, 3-CH,-C,H 4 7.55-6.88(m.811).5.l2~4.79(m. IH).4.31(E) 4.16(2) 425(26), 210(81).168(100), (5.2H).3.8l(s, 311), 2.38(5, 311), l.08(d, 611) 140(53).133(49).45(51) 114 4-CH,OC,H 4 l-C.H, 4-CH,-C,H 4 87-88 7.62-6.98(m, 811), 5.2l~4.82(m, \H).4.29(E) 4\4(Z) 425(14).406(10), 203(100), (s.211).3.82(s, 311).2.35(5, 311). I.08(d.611) 69(27) IIS 4-CH,OC,H 4 i-C,H, 4CH,OC,H 4 L 7.40-6.81 (m.811).5.02-4.83(m.1 H).4.29(E) 4.15(2) 441(30).206(76), 164(100). (s.211).3.8 l(s.311).3.79(s.311). I.08(d.611) 136(42).121(47) 116 4-CH,OC,H 4 1-0,11, 4-F-C.H, L 7.49-6.86(m, 811).5.03~4.84(m. IH).4.30(E) 4.15(2) 429(57).206(36).164(100), (s,2ll), 3.82(5.311), I.IO(d.611) 136(52) 117 4-CH,0-C,ll, i-C,H, 3CIC.II, L 7.49~6.88(m.811).5.03~4.85(m. III), 4.29(E) 4.17(2) 445(62).164(100), 121(42) (s.211).3.82(s.311). I.IO(d.6H) 118 3-CF,-C,H 4 1-0,11, C.H, L 7.80-7.23(m.911).5.l2-4.89(ιn. III).4.30(E) 4.15(2) 449(36), 430(19), 244(100), n (s.211). I.02(d,6ll) 174(40) vo vo © ON Table 4 (Continued) vo vo Dl F vo »^ ° R^ R 4 = CFa (1) Comp. No. R' R l R* sta(e(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 119 3-CF,-C;H 4 l-C,H, 3.4 OCH,OC,H, L 7.95~6.72(m.711).5.95(s.211), 5.28-4.84(m, III). 493(35).244(21).202(100) 4.29(E) 4 I4(2)(J.2H), l.09(d.6H) 120 3CF,-C,H 4 i-C,H, 4-F-C.H, L 7.81 -6.98(m.8H).5.05~4.92(m.1 H).4.29(E) 4.16(2) 467(30), 244(35).203(100). (5.2)1). I.l2(d.611) 174(78).145(65) 121 3-CF,-C,H 4 i-C,H, 3-CI-C,H, L 7.79-7.18(m.8H).5.09~4.89(m.1 H), 4.30(E) 4.14(2) 483(24), 202(100), 174(31) (s.211). l.|0(d.6H) 122 4-F-C,H 4 l-C,H, C,H, 75-76 7.5l-6.9l(m.9H).5.l5-4.67(m.lH).4.29(^4.14(2) 399(70).380(26).194(100), (5.211). I.02(d.611) 152(94), 123(91), 109(36) 123 4-F-C,H 4 l-C,H, 4-CH,-C,H 4 68-69 7.46~6.98(m.8H),5.2l-4.78(m. IH), 4.30(E) 4.15(2) 413(45).394(100).118(36) (s, 211).2.46(s.311). I.07(d.611) 124 4-F-C,H 4 l-C,H, 3-CH,OC,H 4 L 7.5l~6.9l(m.8H).5.5l~4.67(m. III).4.29(^4.17(2) 429(22).410(15).194(47). (s.211).3.85(s.3H), l.02(d.6H) 152(100).124(41) 125 4-F-C,H 4 IC,H, 3-CF,-C,H 4 L 7.79-7.05(m.811).5.23-4.82(m. IH).4.30(E) 4.14(Z) 467(15).194(51).152(100), (5.211). l.08(d.6H) 124(36) 126 4-F-C,H 4 i-0,11, 4 FC.H, L 7.49~6.98(m.8H).5.06-4.87(m. IH). .29(^4.16(^ 417(36), 194(92).152(100), (s,2H). I.ll(d,6ll) 122(86) 127 4-F-C,H 4 i-0,11, 3CIC.H, L 7.4l-7.0l(m.8H).5.02-4.85(m, III).4.30(E) 4.14(Z) 433(45), 152(100).124(41) - (s.211). I.02(d.6ll) o0 128 4-F-C,H 4 i-C,H, CH,S-2-yl L 7.46-6.97(m.711).5.2l-4.75(m, III), 4.29(E) 4.15(2) 405(31).194(36).152(100) (s.211), l.09(d.6H) 122(21), 109(24) VO VO δo Table 4 (Continued) r ■ o R « R 4 = CFa (0 Comp . No . R 1 state(°C) NMR (CDCI,, TMS) δ (ppm) MS (m/c) 129 2-CI-C,H 4 i-C,H, C,H, 758-7.02(m.9H).4.98-4.79(m. I H).4.29(E) 4.15(Z) 415(25).168(100).140(64). (dd.211). l.24(d.3H). I.02(d.3ll) 45(57) 130 2-CI-C,H 4 l-C.H, 3-011,-0,11, 76l-702(m.8H).503~4.79(m. IH).4.3I(E)4.I4(2) 429(60).168(100).140(53) (dd.211).2.35(5.3H). I.24(d.311). I.02(d.311) 131 2-CI-C.H, i-C,H, 4-CH,-C,H 4 7.61 ~7.08(m, 811).4.98-4.79(m. I H).4.30(E) 4.15(2) 429(15), 168(100), 140(44) (dd.2H).2.35(s.3H). I.25(d.311). I.02(d.3H) 132 2-CI-C,H 4 l-C,H, 4-C,H,-C,H 4 7.6O-7.08(m.811).4.98~4.78(m. I H), 4.33(Θ 4.14(.Z) 443(17).210(59).168(100). (dd, 211), 2.65(q, 211), 1.32(1.311). I.25(d.311), 133(86).45(78) co I 03(d.3H) s 133 2-CI-C.H, i-0,11, 3.4-(CH,VC,H, L 7.59-7.02(m.711), 4.98~4.79(nι. III).4.29(E) 4.16(2) 443(20).170(59).168(100). (dd.211).2.26(s.611), l.23(d, 311). I.02(d.311) 140(59) 134 2-CI-C,H 4 i-C,ll, 3.5-(CH,),-C,H, 64-65 7.58~6.89(m.711).5.02-478(m, III), 4.30(E) 4.15(2) 443(30).168(100).140(44) (dd, 211), 2.28(5, 611). I 23(d..Ill), MH)(d, 311) 135 2-CI-C,H 4 i-C,H, 3CH,0-C.H 4 L 7.6O~6.80(m.811), 5.00-4.80(m. IH).4.29(E)4.I7(2) 445(30).210(25).168(100), (dd, 211).3.79(s.311). I.27(d, 311). I.0l(d.311) 140(68).133(56).45(36) 136 2-CI-C,H 4 l-C,H, 4-CH,OC,H 4 L 7.59-687(m, 811), 4.99-478(m. III), 4.32(E) 4.13(2) 445(25).168(100).140(49). (dd, 2H).3.79(s.311). I.25(d, 311). I.03(d.311) 45(78) 137 2CI-C,H 4 l-C,H, 3 FC.H, L 761-69l(m.811), 5 I-4.78(m. III).430(E) 4.18(2) 413(25).210(57).168(100). n (dd,2H), I 28(d.3H). I02(d.311) 140(81).13.1(56) 1.18 2-CI-C.H, i-C,H, 4 FC.H, L 760-698(m.8ll),5.02~4.79(m, III).432(^ 19(2) 433(10).168(100).140(67). vo (dd, 211), I 29(d.311). I03(d.3ll) 133(47) δ © Table 4 (Continued) r o R 4 R 4 = CFa (0 Comp. R 1 R' state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 139 2-CI-C,H 4 i-C,H, 3-CI-C,H 4 L 7.59-7.04(m.811).4.99~4.78(m. IH).4.33(E) 4.16(2) 449(20).168(100), 140(64), (dd,2H). l.25(d.3H). I.02(d.311) 45(75) 140 2-CI-C,H 4 l-C,H, 4-CI-C,II 4 L 7.62-7.l5(m.8H).5.00-4.75(m, III), 4.30(E) 4.17(,2) 449(15).168(100), 140(49), (dd, 211). I.29(d.3H). I.02(d.311) 133(37), 45(34) 141 2CI-C.H, IC,H, 3.5CI,-C,H, L 7.57-7.0l(m.7H),4.97~4.79(m. IH).4.30(E) 4.22(^ 483(25).168(100).140(77). (dd.211). l.23(d.3H). l.02(d,3H) 133(63) 142 3-CI-C,H 4 i-C,H, C,H, 7.65-6.98(m.911), 5.09~4.84(m. Ill), .30(E) .15(2) 415(10), 211(45), 169(100), (5,211). I.09(d.6)l) 87(35) oo 143 3-CI-C,H 4 IC,H, 4-CH,-C,H 4 79-80 7.52~6.53(m.811).5.24-4.72(m. IH).4.29(Q4.I7(^ 429(15), 210(42), 168(100). (s.211).2.34(5, 311), l.2l(d, 611) 140(53).133(41) 144 3-CIC,H 4 iC,H, 4-F-C,H 4 L 7.5l~6.90(m.8H),5.03~4.83(m, III), 4.30(E) 4Λ6(Z) 433(45).210(42).168(100), (s.211), l.08(d.6H) 140(80), 133(32) 145 3-CI-C,H 4 i-C.H, 3-CI-C,H 4 L 7.69-6.95(m, 811).5.09-4.85(m. III).4.31(E) 4.18(2) 449(35).168(100).140(60). (s.2H). I.IO(d.6H) 45(98) • 146 2-CI-4-F-C,H, 1-c.ll, C,H, L 7.45-6.92(m.811).5.0O-4.77(m, IH).4.32(E) 4.19(2) 433(56).193(54).168(65). (dd.211). l.29(d.3H). l.03(d.3H) 151(100).45(46) 147 2 CI-4-F-C,H, i-C.ll, 3CII,-C,H 4 L 7.34-6.98(m,7H).5.0O-4.77(m. IH).4.32(E) 4.17(.Z) 447(35).186(33).84(100). (dd, 211).2.32(s.311). I.27(d, 311). I.0l(d.311) 45(49) o 148 2-CI-4-F-C.H, l-C,H, 4-CH,-C.H 4 L 7.4l-6.99(m,7H),5.0l~4.76(m. IH).4.30(E)4.l6(2r) 447(55).193(67).186(78). (dd.211).2.33(s.311), l.26(d.311). I04(d.311) 151(100).45(35) o vo δ © Table 4 (Continued) Dl F o VO ■δ: R»' VO O ' R R 4 = CFa (1) Comp No. R' R 1 R' state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 'l49 " 2-CI-4-F-C,H, i-C,H, 3.4-(CH,),-C,H, L 7.35-6.97(m.611).5.01 -4.78(m.1 H), 4.30(E) 4.19(2) 461(56), 193(66), 186(88), (dd, 211).2.33(s.611). I.26(d.311), l.02(d, 311) 151(100), 45(49) 150 2-CM-F-C.H, i-c.ll, 3.5-(CH,),-C,H, 70-71 7.38-6.82(m.611).5.00-4.76(m. III).4.31(^4.16(2) 461(31).193(64), 186(85), (dd, 2H).2.30(s.6H). I.27(d.311), l.00(d, 311) 151(100), 45(54) ISI 2-Cl-4F-C,H, iC.H, 3-F-C,H 4 L 7.40~6.95(m, 7H), 5.00~4.79(m.1 H).4.31(E) 4.17(2) 451(40).193(61), 186(66). (dd, 211). I.27(d.3ll). I.03(d.3ll) 151(100), 45(48) 152 2-CI-4-F-C,H, 1-C.H, 4-F-C,H 4 L 7.47-6.94(m, 711).5.00~4.78(m.1 H).4.32(E) 4.16(Z) 451(22), 19.1(52), 186(73), (dd.211). I.26(d.311). I.02(d, 311) 151(100).45(53) 153 2-CI-4-F-C,H, i-C,H, 3-CI-C,H 4 L 7.45-6.98(m.7H).5.0O~4.79(m. IH).4.32(E) .16(2) 467(39), 193(69), 186(74). (dd.2H). l.28(d.3H). I.04(d.3ll) 151(100), 45(53) oo 154 2CI-4F-C,H, i-C,H, 4-OC,H 4 L 7.44-6.98(m, 11), 4.98~4.75(m, IH), 4.30(E) 4.17(2) 467(35).193(71).186(72), c» (dd, 211). I.27(d, 311). I.03(d, 311) 151(100).45(60) 155 2-CI-4-F-C,H, i-C,H, 3.5-01,-0,11, L 7.45-7.0l(m.611).5.00~4.78(m. III).4.32(E) 4.15(2) 501(41).193(87).186(76). (dd, 211). I.27(d.3li). I.03(d.3ll) 151(100).45(68) 156 3.4-0,-0,11, 1-C.H, C,H, 96-97 760-6.87(m.811), 504~4.84(m. III).4.30(E) 4.15(2) 449(30), 244(31).202(100). (s,2ll), l.07(d.611) 167(83).45(65) 157 3.4-01,-0,11, i-C,H, 3FC,H 4 74-75 7.6l-6.95(m.711).5.05-485(m. IH).4.29(E) 4.14(2) 467(36).244(28), 202(100), (5,211), I.l2(d.6ll) ' 174(51), 167(82), 45(68) 158 3,4-01,0,11, 1-C.H, 4-F-C,H L 7.59-6.87(m.711).5.03~4.84(m. III).4.30(E) 4.16(2) 467(20), 202(98), 167(100) (s.211). I.09(d.6ll) n 159 3,4CI,-C,H, i-C,H, 3CIC.H, L 7.60-6.92(m.7H).5.02-4.82(m. IH).4.31(C) 4Λ5(Z) 483(42).244(65), 204(100). (s.211), I 08(d.611) 167(72) o 160 3.4-CI,-C.H, i-0,11, CIC.II, 44-45 7.70-690(111.711), 5.02-485(111, III).4.30(E) 4.15(2) 483(12).244(39), 202(100). v vo (5,211), l.07(d,6ll) 167(54).45(48) δ © 161 3.4-CI,-C,H i-C,H, 3.5-0,-0,11, 80-81 7.6l-6.95(m,6H).505-486(m. IH), 4.28(E) 4.14(2) 517(8).202(99).167(89). (s.211), l.09(d,6H) 45(100) Table 4 (Continued) ϊ; R 1 F O R ' 4 R 4 = CFa (I) Comp . No . R 1 π J state( r ) NMIKCDClj, TMS) δ (ppm) MS (in/e) 367(15), 162(100), 147(34). 162 3-CH3-G.H4 Cl b Cel ls L 7.45-6.90(m, 911), 4.41 (s, 211), 3.27(s, 311), 2.36(s, 310 91(32) 163 3-CH 3 -C 6 H 4 CH3 7.32-6.90(m, 8H), 4.39(s, 211), 3.26(s, 3H), 2.36(s, 311). 4-CH3-C6II4 54 381(13), 162(100), 147(37), 2.34(s, 311) 91(34) 164 3-CH3-C6H< 7.48^.79(m, 8H), 4.43(s, 211), 3.82(s, 311), 3.48(s. 3H), CH3 4-CH3O-C5H4 69 397(15), 162(100), 134(42), 2.64(s, 311) 91(42). 43(39) 165 3-CH3-C6H4 Clb 4-F-C6H L 7.44 3.93(m, 811), 4.41(s, 211), 3.27(s, 3H), 2.38(s, 3H) 385(16). 162(100), 147(60), 134(74). 91(65) o 166 3-CH3-C6H CH3 3-CF3-C6H L 7.82-6.98(m, 8H), 4.49(s, 211), 3.28(s, 3H), 3.39(s, 311) 435(25), 162(100), 147(69), 134(64), 91(69) 167 3-CH3-C6H4 CH3 4-CI-C6H4 L 7.406.97(m, 8H), 4.42(s, 211), 3.28(s, 3H), 2.39(s, 311) 401(12). 162(100), 147(50). 134(56), 91(48) 168 4-CIb-C6H CII3 Cells 90 7.446.99(m, 910, 4.40(s, 210, 3.26(s. 310. 2.38(s, 3H) 367(15), 162(100), 147(48), 134(46), 91(47) 169 L 7.30-6.99(m, 810, 4.41 (s, 210, 3.27(s, 310. 2.39(s, 310. .381(14), 162(100). 147(46). 4-CH3-C6H4 CH3 3-CH3-C6H 2.36(s, 310 134(36), 91 (32) 170 4-CH3-C6H4 7.33-6.99(m, 810, 4.39(s, 210, 3.28(s, 310, 2.38(s, 310, Clb 4-CH3-C6I I4 108 .381(13), 162(100), 147(41), 2.35(s, 311) 134(36), 91 (27) o 171 4-CH3-C6H4 Clb 4-ClbO-C«H4 83 7.36-6.90(m, 810, 4.38(s, 210, 3.80(s, 310, 3.28(s. 310, 397(25), 162(100), 147(42), 2.37(s, 31 134(44), 91(43) vo vo δ o Table 4 (Continued) o .fe. R 4 = CFa (0 Comp . No . R 1 R' R J state (t) NMIUCDCb, TMS) δ (ppm) MS (m e) 385(23), 162(100), 134(46), 172 4-CIb-CbH4 Clb 4-F-C-H4 71 7 4-699(m, 810, 4 40(s, 210, 327(s, 3H), 238(s. 310 91(26) 173 743 702(m, 8H), 4 42(s, 210, 327(s, 310, 238(s, 3H) 401(11 ), 162(100), 147(48), 4-CH3-C6H4 Clb 3-CI-C6H L 134(38), 91(36) 174 735-704(m, 710, 4.45(s, 210, 328(s, 3H), 239(s, 310 4-CIb-C6H4 CH3 3,5-Cl 2 -C6lb L 435(15), 162(100). 147(54), 134(50) 175 4-CH3-C6H4 C6)feO-CβH4 80 7 0-694(m, 1310, 435(s, 210, 327(s, 310, 2.39(s, 310 459(15), 162(100), 147(33), CH3 4- o 134(28) 176 4-Clb-CbH4 Clb 7 26H3 77(ΓΠ, 7H), 595(s, 210, 4 40(s, 2H), 327(s, 310, 3,4-OCH θ-C6H 68 411(15), 162(100), 147(39), 238(s, 310 134(32) 177 Celt L 45- 689(m. 810, 442(s, 210, 327(s. 3H), 228(s, 310, 381(13). 161(33). 86(72), 3,4-(CH3) 2 -C6ll3 Clb 227(s, 310 .84(100) 178 3,4-(CH 3 )2-C6lb CH3 4-Clb-CJl« L 734 690(m, 710. 4 41 (s, 210, 325(s, 3)0, 230(s. 3H), 395(12), 176( 100), 161 (96), 228(s, 310, 226(s, 310 43(49) 179 3,5-(CH3) 2 -C6lb L 724-6.36(m, 610, 4 37(s, 210, 322(s, 310, 228(s, 610, 3,4-(CH3)2-C6lb Clb 225(s, 310, 231 (s, 311) 409(19), 176(100), 161(65) 1 180 C6ll4 L 737-088(m, 710, 441(s, 210, 326(s, 310, 265(q, 210, 3,4-(CIb) 2 -C6lb Clb 4-C2lb- 230(s, 310, 228(s, 310, 1 26(t, 310 409(24), 176(100), 161(58) π3 181 3,4-(Clb)2-C6H3 Clb 4-F-CβH4 L 7 3^ 83(m, 710. 4 41 (s, 210, 325(s, 310, 226(s. 6H) 399(18), 176(100), 161(99), 132(22) vo — o © Table 4 (Continued) vo vo R 1 F * O {,-• R 4 = CFa (I) Comp . No . R 1 R 2 n J state(C) NMR(CDC , TMS) δ (ppm) MS (m/e) 182 7.696.86(m, 449(61), 176(100), 161(84) 3,4-(CIb) 2 -C«lb Clb 4-CF3-C6II4 L 710, 4.39(s. 2)0, 3.27(s, 310, 2.89(s, 310. 2.27(s, 310 183 7.326.81 (m, 3,4-(CH 3 ) 2 -C€lb 710, 4.42(s, 210, 3.26(s, 310, 2.29(s, 310, 415(12), 176(97). 161(100), Clb 3-CI-UH4 L 2.28(s, 310 .84(42) 184 3,4-(CH 3 ) 2 -C«lb 7.406.85(m, 1210, 4.42(s, 210, 3.26(s, 310, 2.28(s, 310, 473(25), 176(100), 161(76) Clb 4-C«lkOG,H, L 2.27(s, 311) I lffi 7.46-6.78(m, 3,4-(CIb) 2 -C6lb 810, s £δ 4.96(m, 110, 4.30(s. 2H), 2.31 (s, 310, 409(36), 204(41), 162(100), 1-C3H7 Cell 2.29(s, 310, 1.06(d, 611) 1.34(40) 186 7.27-θ.77(m, 710, 4.95(m, I II), 4.24(s, 210, 2.35(s, 310, 423(48), 204(51), 162(100), 3,4-(Clb) 2 -C6lb 1-C3H7 4-CH3-C6H4 L 2.29(s, 310, 2.27(s, 310, 1.05(d, 611) 134(33) 187 7.45-6.78(m, 710, 4.93(m, 111), 4.25(s, 2H), 2.28(s, 311), 3,4-(CIb)2-CeIb 427(14), 204(37), 162(100). 1-C3H7 4-F-CeH4 52 2.26(s, 310, 1.06(d, 610 134(34) 188 58 7.43-6.79(m, 710, 4.94(m, 111), 4.26(s, 210, 2.29(s, 310, 443(18), 204(33), 162(100), 3,4-(CH 3 )2-C6H3 1-C3H7 3-CI-C6H4 2.27(s, 310, 1.06(d, 610 134(35) 189 7.44-6.90(m, 810, 4.39(s, 210, 3.82(s, 310, 3.25(s, 311) 401(18), 178(100), 147(66), 4-C ) bO-C6ll4 Clb 4-F-C6H4 L 121(53) 190 7.42-7.03(m, 910. 4.41(s, 210, 3.29(s, 310 .387(14), 182(51), 147(100), 3-C1-C6Ϊ14 Clb Cells L 118(20) n 191 H4 L 7.43-7.16(m, 810, 4.34(s, 210, 3.27(s, 310, 2.35(s, 310 401(14), 182(47), 147(100), 3-CI-CβH4 Clb 3-CHa-Cβ 118(20) o o δ © Table 4 (Continued) *: R 4 = CFa (•) Comp . No . R 1 R< R J state( t) NMIKCDCIj, TMS) δ (ppm) MS (m/e) 192 3-CI-C6H lb 7.41-7.01 (m, 710, 4.39(s, 210, 3.27(s, 310, 2.25(s, 611) 415(17), 182(64), 147(100) 3,4- ( CIb ) 2 -G i b L 193 3-CI-C6lb Clb 4-C 2 Ib-C6l l4 L 7.42-7.02(m, 810, 4.40(s, 210, 3.26(s, 310, 2.ι34(q, 210, 415(21 ), 182(99), 147(100) 1.26(t, 311) 194 3-CI-C6H -C6H4 L 7.42-7.02(m, 810, 4.41 (s, 210, 3.28(s, 3H), 1.31 (s, 911) Clb 4-t-C4ll9 443(18), 182(72). 147(100) 195 3-Cl-CβH4 H3O-C6H4 L 7.43-6.87(m, 810, 4.40(s, 210, 3.81(s, 3H), 3.29(s, 310 Clb 4-C 417(15), 182(52), 147(100), 78(19) t 196 3-CI-C6H4 CH3 3-F-Cύh L 7.43-7.02(m, 810, 4.44(s, 210, 3.30(s, 3H) 405(17). 182(38). 147(100) 197 3-CI-C6H 7.43-7.00(m, 810, 4.36(s, 210, 3.29(s, 310 CHa 4-F-CβH4 L 405(30), 147(46), 85(60). .84(100), 43(51) 198 3-CI-G.H4 Clb 4-CI-C45H4 7.42-7.06(m, 810, 4.43(s, 210, 3.28(s, 310 421 (13), 182(40), 147(100), 43(26) 199 4-CI-C6H4 Clb Cells 95 7.46-7.09(m, 910, 4.39(s, 2H), 3.29(s, 310 387(10), 181(28), 147(100) 200 CH3 3-CIb-GJl4 74 7.47-7.05(m, 810, 4.39(s, 210, 3.25(s, 310, 2.35(s, 310 401(19). 182(48), 147(100) 4-CI-C6H O H 201 4-CI-C6H Clb 4-CIb-Gill4 99 7.48 7.06(m, 811), 4.38(s, 210, 3.26(s, 310, 2.^(s, 310 401(18), 147(71). 84(100). 47(83) vo δ © Table 4 ( Continued ) vo vo ii ^ > R 1 F I 1 R 2 O ' R < R 4 = CFa 0) Comp . No . n 1 R' R J state ( C) NMIHCDCb, TMS) <J (ppm) MS (m/e) 202 s, 310, 2.22(s, 610 415(15), 182(59), 147(100) 4-CI-C6H4 Clb 3,4- ( Clb) 2 -C6l b 76 7.43-7.02(m, 710, 4.35(s, 210, 3.24( 203 .64(q, 210, 415(14), 182(47). 147(100), 4-CI-C6H4 Clb 4-C2lb-C6ll 85 7.46-7.04(m, 810, 4.38(s, 210, 3.25(s, 310, 2 1.22U, 310 118(24) 204 0, 4.40(s, 210, 3.81(s, 310, 3.26(s. 31 4-CI-C6H4 Clb 3-CH3O-G3H4 L 7.43-6.85(m, 81 0 417(19), 182(23), 147(100) 205 3.26(s, 3H) 417(16), 182(47). 147(100) 4-CI-C6H4 CH3 4-CH3O-C6H4 90 7.43^.86(m, 810, 4.31 (s, 2H). 3.80(s, 310; (100) 206 4-CI-C6H4 Clb 3-F-G3H4 L 7.47-7.01 (m, 811), 4.42(s, 210, 3.28(s, 310 405(17), 182(42), 147 207 4-CI-C6H4 Clb 4-F-CeH4 72 7.48-7.00(m, 810, 4.40(s, 210, 3.26(s, 310 405(18), 182(77), 147(100) 208 7.09(m, 810, 4.41(s, 210, 3.27(s. 310 421(15), 182(45), 147(100) 4-CI-C43H4 Clb 3-Cl-C>5H4 L 7.47- 209 41(s, 210, 3.28(s, 310 421(18), 182(29 4-CI-C6H4 Clb 4-Cl-CβH4 66 7.47-7.09(m, 810, 4. ), 147(100), 118(29) 210 thiophene-2-yl L 7.47-6.99(m, 710, 4.45(s, 2H). 3.28(s, 310 393(24), 182(62), 147(100) 4-CI-C6H4 CH3 "13 O H 73 vo vo δ s Table 4 (Continued) o o ^1 vo R 1 F 1 1 ^"γ^o ^" 1 0 R 4 R 4 = CFΛFa (1) Comp . NO . R' R 2 R J state(C) NMR(CDCI 3 , TMS) <J (ppm) MS (m/e) 211 Cells Clb Celb L 7.51-7.04(m, 1010, 4.32(s, 210, 3.28(s, 3H) 403(23), 147(100), 120(94). 91(40) 212 CeHs q, 210, 1.10(t. 3H) 417(24), 162(100), 134(94), Calls Celb L 7.49-7.01(m, 1010, 4.28(s, 210, 3.75( 106(71). 91(62), 77(57) 7.5O-7.02(m, 1011), 4.21(s, 2H), 3.67(t, 211), 1.67-1.45 431(63), 180(65), 133(60), 213 Cells n-Cslfc CeHs L (m. 211). 0.91 (t, 3H) 106(100) 214 Celt 1-C3H7 Celb L 7.51-7.00(m. 1010. 4.98(m. Ill), 4.10(s, 211), 1.09(d, 6H) 431(24). 176(62). 133(100), 120(49) t» 215 71(q, 2H), 4-CIbO-Cell4 Czlls 447(55), 324(53), 239(52), Celb L 7.46-6.84(m. 910, 4.19(s, 210, 3.81(s, 310, 3. l.l Kt, 310 149(100). 135(55), 120(41) 216 , 310, 3.65(t, 210, 461(43), 206(100), 136(37), 4-ClbO-CeH4 n-C 3 ll7 GHs L 7.47-6.87(m, 910, 4.26(s, 210, 3.82(s 1.67 1.45(m, 210, 0.90(t, 310 121(54) 217 3-CF3-G.H4 7.76-7.16(m, 910, 4 d, 610 499(∞), 244(46), 202(100), 1-C3H7 Cells L .94(m. Ill), 4.08(s, 210, 1.08( 174(66), 145(26), 43(74) 218 4-F-CeH4 -C3H7 CeHs L 7.46-6.97(m, 910, 4.97(m, 111), 4.15(s, 210, 1.02(d, 610 449(21), 194(33), 152(100), 124(45) 219 3.74(q, 210, 1.10(t, 310 4-CI-C6H C 2 Hs Cells L 7.49-7.01(m. 910, 4.20(s, 210, 451(57), 324(47), 219(52), -13 182(78), 154(100), 139(42) O H 7.54-7.01(m, 810, 4.20(s, 210, 3.21(s, 310 471(41), 436(73), 181(100) o vo δ4© - 45 - Example 221 : Preparation of -2 - ( 2 ' -f luoro- 1 ' - t r i f l u o r o m e t h y l s t y r y l - 2 ' - oxy )acetylpiperidine (Compound 221) The procedure of Example 1 was repeated except that 286 mg(2 mmol) of M-2-hydroxyacetylpiperidine obtained in Preparation 32 and 2 , 2-difluoro-1-trifluoromethyl styrene obtained in Preparation 56 were used and that silica gel column chromatography was conducted using a mixture of n- hexane and ethyl acetate(2:l) as an eluent to obtain 600 mg(yield 90.6%) of the title compound as a white solid. 1 H-NMR (CDC1 3 , TMS) δ: 7.58-7.17(m, 5H), 4.79 (E isomer ) 4.67 (Z. isomer) (s, 2H), 3.17-3.05 (m, 4H), 1.78-1.35(m, 6H) MS (m/e): 331(M + , 40), 126(85), 98(76), 84(100) 9 F-NMR (CDCI 3 , CFCI 3 ) δ: -57.38(2. isomer) -57.83(E isomer) (d,3F) , -82.24(E isomer) -84.28(-i isomer) (q, IF) m.p.: 78-79 °C Examples 222 to 294 Using each of the alcoholic compounds obtained in Preparations 32 to 48 and each of the fluorovinyl compounds obtained in Preparations 49 to 56 and 58 to 65, the procedure of Example 221 was repeated to obtain 73 compounds (Compounds 222 to 294) of formula (I) of the present invention having various R , R 2 and R 3 groups listed in Table 5. The 1 H-NMR and MS data and melting points of these compounds are also shown in Table 5. L in Table 5 represents liquid. Table 5 vo o ≥ R 1 F R^ N γ^O^ R3 0 R 4 R 4 =CF 3 (0 Comp . No . R 1 R 2 R 3 state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 221 -(CH 2 ),- C.H, 78-79 7.58-7.17(m. 5H), 4.79(E) 4.67(Z) (s. 211). 3.71-3.05 331(40), 126(85). 98(76), (m.4H), l.78~l.35(m, 6H) 84(100) 222 -(CH 2 ) S - 3-CH, C t H 4 L 7.3 l~7.04(m.4H), 4.78(E) 4.66(Z)(s, 2H), 3.64-3.03 345(26), 126(71). 98(70), (m, 4H), 2.37(s, 3H), IJ4~l.38(m, 6H) 84(100) 223 -(CH,),- 4 CH,-C 6 H 4 L 7.43-7.02(m, 4H), 4.79(E) 4.67(Z)(s, 2H), 3.64-3.01 345(23), 326(18). 126(34), (m, 4H), 2.43(s, 3H), 1.98- 1.17(m, 6H) 98(100), 84(94) 224 -(CH,),- 4^ 2 H,-C,H 4 L 7.41-7.13(m.4H), 4.77(E) 4.68(2)(s, 2H), 3.61 -3.06 359(11), 126(100).98(51), (m, 4H), 2.64(q. 2H), l.72~l .38(m. 6H), 1.25(1, 3H) 84(61) σ. 225 (CH 2 ) 5 - 3.4-(CH i ) 1 -C 1 H i L 7.21 -7.00(m, 3H), 4.79(E) 4.67(Z)(s, 2H), 3.60-3.04 359(36), 126(85), 98(41 ). (m, 4H), 2.23(s, 6H), 1.70- 1.37(m, 6HJ 84( 100).42(30) 226 -(CH 2 ) 5 - 3,5-(CH,) 2 -C 6 H, L 7.03-6.87(m. 3H), 4.7i(E) 4.66(Z)(s, 211), 3.59-3.01 359(40). 126(55). 98(63), (m, 4H), 2.26(s.6H). 1.69- 1.34(m.6H) 84(100).42(57) 227 -(CH 2 ),- 3-CH,O C 4 H 4 L 7.48-6.72(m, 4H).4.78(15) 4.66(Z)(s, 2H). 3.82(s, 3H), 361(23), 126(33). 98(83). 3.78-2.98(m, 4H), 1.82- 1 43(m, 6H) 84( 100) 228 (CH 2 ),- 4-CII,0-C 6 H 4 L 7 52-6.75(m, 4H), 4.79(E) 4.66(2)(s, 2H), 3.84(s, 3H), 361 (50), 157(44), 126( 100), 3.78-3 0I(m, 4H), 1 84~l .36(m, 6H) 98(92), 84(78), 55(69) O H 229 -(CH 2 ),- 3,4-OCH 2 0-C t H, 6.94-6.75(m, 3H), 5.94(s, 2H), 4.78(E) 4.65(Z)(s, 2H). 375(50). 126(53).98(60). 3 63-3.00(ιn, 4H), l .70~ l.44(m, 6H) 84( 100). 43(90) o vo 230 (CH 2 ),- 3-CF,-C 6 H 4 L 7.72~7.32(m, 411). 4.79(E) 4.65(Z)(s, 211), 3.74-3.02 399(87), 212(47). 127( 100) © o (m, 4H), 1.97- I. I 8( , 6H) Table 5(Continued) ≥: I < * 3 o R 4 =CF, (i) Comp. No. J R 3 state(°C) NMR (CDCI,, TMS) 8 (ppm) MS (m/e) 231 -(CH 2 ),- 3-F-C 6 H 4 L 7.62-6.89(m, 4H).4.80(E) 4.68(Z)(s.2H).3.75-3.04 349(47), 126(64).98(100). (m,4H), l.78~ά94(m.6H) 84(78) 232 -(CH 2 ) 5 - 4-F-C 6 H 4 L 7.51 ~6.95(m, 4H), 4.79(E) 4.67(Z)(s, 2H).3.62-3.12 349(60), 126(66), 98(56), (m.4H), l.73~l.45(m.6H) 84(100).42(55) 233 -(CH 2 ),- 3-CI-C-H L 7.49-7.17(m, 4H), 4.80(E) 4.67(Z)(s, 2H).3.61-3.07 365(35), 126(32), 98(20), (m,4H). IJ2-l.42(m,6H) 84(100), 42(38) 234 -(CH 2 ),- 4-CI-C,H 4 L 7.78~7.34(m, 4H), 4.79(E) 4.66(Z)(s, 211), 3.85-3.02 365(20).126(57), 98(41), (m.4H).1.83~l.42(m,6H) 84(100), 45(69) 235 -(CH 2 ),- 3,5-CI 2 -C 6 H, 54-55 7.39-7.15(m.3H).4.81(E) 4.70(Z)(s.2H).3.60-3.08 399(41), 126(60), 98(42), (m.4H), 1.78~l.36(m.6H) 84(100) 236 -(CH 2 ) C 4 H,S-2-yl L 7.47~6.94(m, 3H).4.80(E) 4.70(Z)(s, 211), 3.82-3.07 337(10), 126(100).98(74). (m,4H), 1.81~1.42(m,6H) 84(80) 237 -CH(CH,)(CII 2 ) 4 - C 4 H, L 7.63-7.18(m, 5H), 4.83(E) 4.74(Z)(s.2H), 3.25-2.76 345(46), 140(52).98(100). (m.3H). I.95~l.48(m.6H).1.26(d.3H) 84(46).55(63) o3 238 -CH(CH 3 )(CH 2 ) 4 - 3-CH,-QH 4 L 7.44-6.92(m, 4H).4.82(E) 4.75(Z)(s, 2H), 3.18-2.72 359(65).242(40), 98(78), π (m, 3H).2.35(s.311), l.95~l.46(m,6H), l.29(d,3ll) 84(92).56(100) vo 23S -CH(CH t )(CH 2 )- 4-CH 1 -C ( H 4 L 7.44-7.03(m.4H), 4.80(E) 4.74(Z)(s, 2H), 3.82-2.45 359(15), 140(66), 98(100) (m,3H),2.42($,3ll), 1.86~l.42(m,6H), l.l2(d,3H) o 240 -CH(CH.)(CH 2 ) 4 - 3.4-(CH,) 2 CH, L 7.3l~7.03(m, 3H), 4.81(E) 4.74(Z)(s.2H).3.24-2.75 373(30), 140(86), 98(100), (m, 3H), 2.2R(s, 6H), 1.96~l.45(m, 611). I.28(d.3H) 55(75) Table 5(Continued) vo .fe. vo R^ N γ^o^y R J 0 R4 R 4 =CF, (I) Comp. No. R! R 2 R 3 state (°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 241 -CH(CH,)(CII 2 ) 4 - IMCH -CJtl, 7.28-6.83(m, 3H), 4.80(E) 4.75(Z)(s.2H).3.25-2J4 373(24), 140(89), 98(100), (m, 3H), 2.29(s, 6H), l.96~1.44(m, 6H), l.26(d, 3H) 55(76) 242 -CH(CH,)(CH 2 ) 4 - 4-C 2 H,-C 6 H 4 7.52-7.05(m, 4H), 4.81 (E) 4.76(Z)(s, 211).3.24-2.85 373(45), 140(43), 98(100). (m, 3H).2.71 (q, 2H), !.95~1.45(m, 6H). I.28(t.3H), 55(43) l l (d,3H) 243 -CH(CH,)(CH 2 ) 4 - 3CH,0-C 6 H 4 7.47-6.74(m, 4H), 4.79(E) 4.74(Z)(s, 2H), 3.78(s, 3H), 375(20).140(97).98(100), 3.24~2.73(m, 3H), 1.95-1.3(m.611). l.24(d,3H) 55(84) 244 -CH(CH,)(CH 2 ) 4 - 4CH,0-C 6 H 4 7.54-6.79(m, 4H).4.80(E) 4.76(Z)(s, 2H).3.87(s, 3H), 375(20), 140(56), 98(100), 3.22-2.91 (m,3H), l.97~l.48(m,l5H), l.33(d, 3H) 56(32) 2 " 45 -cn(αι,και,) 4 - 3,4-OCH j O-C j ll, 7.20~6.62(m, 3H), 6.0l(s, 2H), 4.79(E) 4.75(Z)(s, 2H), 389(19), 219(40), 140(87), 3.23~2.74(m, 3H). l.97~l.49(m,6H), l.29(d,3H) 112(74), 98(100), 55(77) 246 -CH(CH,)(CH 2 ) 4 - S-CF j - H, 7.76~7.37(m.4H), 4.78(E) 4.73(Z)(s.2H).3.25-2.72 413(51), M0(29), 98(62), (m, 3H). I.96~l.42(m, 6H), l.23(d, 3H) 84(69).43(100) 2 7 -CH(CH,)(CH 2 ) 4 - 3-F- H 4 7.53~6.78(m, 411), 4.79(E) 4.74(Z)(s, 2H), 3.24-2.75 363(38).140(38).98(100). (m, 3H), l.96~l.46(m, 611), l.25(d, 3H) 55(45) o 248 -CH(CH,)(CH 2 ) 4 - 4-F-QH, 7.65~6.82(m, 4H).4.81 (E) 4.75(Z)(s.2H).3.28-2.65 363(50).140(78).112(46), (m,3H), l.95-l.34(m.6H), I.l6(d,3ll) 98(100).55(57) vo 249 -CH(CH,)(CH 2 ) 4 - 3-Cl-C„H 4 7.58~7.28(m.4H).4.80(E) 4.75(Z)(s, 2H), 3.21-2.94 379(72), 140(44).98(100). (m, 311), 1.9R-I.49(in, 611), l.32(d,3H) 56(57) 250 -CII(CH,)(CH,) 4 - 4-CI-C I, 7.57-7.l8(ni, 4H), 4.81(G) 4.74(Z)(s, 2H).3.18-2.74 379(35), 140(70).98(100), (m,3H), l.75-l.35(in, 6H), 1.15(d.311) 55(47) Table 5(Continued) vo O VO y F *' R 4 R 4 =CF 3 (l) Comp . No . R1 R2 R 3 state(°C) NMR (CDCI,, TMS) δ (ppm) MS (m/e) 251 -CH(CH,)(CH 2 ) 4 - 3,5-CI 2 -C 6 H, L 7.64-7.18(m, 3H), 4.80(E) 4.75(Z)(s, 2H), 3.24-2.75 413(35). 140(49), 98( 100), (m.3H). I.95~1.44(m, 6H), l.23(d, 3H) 55(57) 252 -CH(CH,)(CH 2 ) 4 - C 4 H,S-2-yl L 7.45-6.9l(m, 3H), 4.79(E) 4.74(2)(s, 211), 3.26-2.73 351(20). 140(65), 98( 100). (m, 3H), 1.97-l.4 l(m, 6H), l .24(d, 3H) 55(66). 41(47) , 253 -CH(C 2 H 5 )(CH 2 ) 4 - C 6 H, L 7.48-7.22(m, 511).4MB) 4.75(2)(s. 211), 3.58-2.62 359(18), 154(100), 126(58) (m, 311), 1.81-1.2 l(m, 8H), 0.83(1.311) 1 12(98) 254 -CH(C 2 H,)(CH 2 ) 4 - 4 CH, C 6 H 4 L 7.43~7.02(m, 4H), 4.81(E) 4.76(2)(s. 2H), 4.01-2.52 373(30), 354(15). 154(43), (m. 3H), 2.41 (s, 3H). 1.98- 1.12(m, 8H), 0.92(t, 3H) 1 12(100) 255 -CH(C 2 H,)(CH 2 ) 4 - 3-CI C,H 4 L 7.59-7.15(m.4H).4.80(E) 4.75(.Z)(s, 2H).4.54-3.91 393(71), 154(41), 1 12( 100) (m, 211). 3.43~3.I2(m. 3H). I.95- I.23(m. 6H), l.04(t, 3H) 97(38).55(61) 256 -CH(CH,)(CH 2 ),CH(CH,)- 4-CH,- H 4 L 7.49-7.0 l(m, 4H), 4.80(φ 4.74(^(s. 211), 4.54-3.96 373(49), 354(21). 217( 100) ( , 2H).2.42(s, 3H), l .98~i .5l(m, 6H). I.42(d.6H) 153(48).69(21) 257 -CH(CH,)(CH 2 ),CH(CH,)- 3-CI-C 6 H 4 58-59 7.62-7.18(m. 4H).4.8 i (E) 4.75(Z)(s, 211), 3.75-2.76 393(60). 154(30), 1 12( 100) (m, 2H). l .98-1.48(m, 6H). l.42(d. 6H) 69(45). 55(62) 258 -CH(CH,)(CH 2 ),CH(CH,)- 3,5-CI 2 -C,H, 98-99 7.45-7.2 l(m, 3H).4 WE) 4.76(Z)(s, 2H), 3.78-3.54 427(20). 154(60), 112(100) n (m, 2H). l .98-1.47(m, 6H), 1.28(d, 6H) 69(64), 55(80) 259 (CH 2 ) j CH=CHCH 2 - 4-CH,-C 6 H 4 L 7.5 l~7. IO(m, 4H), 5.92-5.62(m, 2H).4.81(15) 4.74(2) 343( 10). 324(48). 124(74). vo vo (s. 2H), 4.l8-3.32(m, 4H), 2.43(s. 3H). 2.42-1.9 l(m.,2H) 96(42), 82(100) o 260 -(CH 2 ) 2 0(CH 2 ) 2 - H 5 L 7.42~7.23(m. 5H), 4.80(E) 4.75(Z)(s, 2H), 3.72-3.10 333( 10), 129(69). 102( 100) σv (m.8ll) 87(30) Table 5 (Continued) vo ϊ; R 1 F j 1 κ y O R 4 R 4 =CF 3 (I) Comp . No . R 1 R 2 R 3 state(°C) NMR (CDCI,, TMS) δ (ppm) MS (m/e) 261 -(CH 2 ) 2 0(CH 2 V 4-CH,-C H 4 75-76 7.43~7.02(m, 4H), 4.81 (E) 4.76(Z)(s, 2H), 4.02-3.10 347(15), 128(48), 100(100) (m, 8H), 2.41(s. 3H) 262 -(CH 2 ) C(C 4 H )C- H, 72-73 7.45-7.10(m.9H).4.80(.E) 4.74(2)(s, 2H), 3.79(t, 2H), 379(14). 360( 15), 174(70). 2.70(1, 2H), 2.06- 1.87(m, 2H) 146(70). 118(100) ' 263 -(CH 2 ),C(C 4 H 4 )C- 4 CH C t H 4 L 7.49~7.02(m. 8H), 4.8 \(E) 4.76(Z)(s, 2H), 3.78(1, 2H). 393(38). 374(28). 174(89). 2.71(1, 2H). 2.42(s, 311). 2.05-1.86(m. 2H) 146(96), 1 18( 100) 264 -(CH 2 ) 6 - C.H, L 7.50-7.25(m. 5H).4 80(E) 4.75(^(s, 2H), 3.60-3.10 345(16). 147(100), 1 12(46) (m.4H), l.8 l~l.45(m, 8H) 99(26) i 265 -<CH 2 ) - 3-CH,-C t H L 7 38-7.08(m, 4H).4.81(H) 4.76(Z)(s. 2H). 3.60-3.13 359(15), 140(44), 98(100), σ (m, 411), 2.3 l(s, 3H), l.78-l.38(m. 8H) 43(63) 266 (CH 2 ) r 4-CH,-C <l H 4 L 7.40-7. IO(m, 4H), 4.80(E) 4.75(^(s, 2H), 3.61-3.17 359(13), 140(56), 97(53). ( , 4H), 2.38(s.3H). 1.81 - 1.48(m, 8H) 55(53), 43(100) 267 -(CH 2 ) 6 - 4-C 2 H,-C 6 H 4 L 7.40-7.12(m, 4H), 4.81 (E) 4.75(Z)(s. 211). 3.60-3.15 373(23), 140(100), 98(54) (m.4H). 2.65(q. 2H). l.85-l .48(m. 8H), 1.26(1, 311) 268 -(CH 2 ) 6 - 3,4-(CH,) 2 -C,H, L 7.24~7.02(m, 3H), 4.79(E) 4.74(2)(s, 2H), 3.58-3.1 1 373(71), 140(51).98(100) ■■ a (m, 4H), 2.32(s, 611). 1.77- 1.41 (m. 811) n H 269 -(CH 2 ) 6 - s.s-tci -c.n, L 706-6. l(m, 3H), 4 80(E) 4.75(2)(s, 211), 3.60-3.12 373(31 ). 140(39), 98( 100), (m, 4H), 2 30(s, 6H), 1.80~1.44(m, 8H) 42(39) o vo 270 -(CHΛ- 3 C1I,0-C 6 H 4 L 7.29~6.76(m, 4H), 4 80(E) 4.75(Z)(s, 211), 3.74(s, 311), 375(53), 140(55), 98( 100), o o 3.54-3.10(m, 411), 1 78-1 42(m, 811) 43(56) Table 5(Continued) VO VO 4 R 1 F j 1 R»" 0 R 4 R =CF 3 (i) Comp. No. R 1 R 2 R 3 state(°C) NMR (CDCI,. TMS) δ (ppm) MS (m/e) 271 -(CH 2 ) 6 - 4CH,0-C 4 H 4 L 7.38~6.80(m.4H).4.79(E) 4.74(Z)(s.2H).3.76(s.311). 375(21), 140(29).98(44). 3.58-3. l2(m,4H).1.8l-1.46(m,8H) 59(38).43(100) 272 •(CH,V 3,4-OCH 2 0-C 6 H, L 7.l5~6.78(m, 3H), 5.97(s, 2H), 4.80(E) 4.75(Z)(s, 2H), 389(13).140(70), 98(100) 3.75-3 l4(m,4H), 1.98-l.32(m,8H) 273 -(CH 2 ) 6 - 3-F-C,H 4 L 7.40-6.98(m, 4H), 4.79(E) 4.74(Z)(s, 211), 3.61 -3.16 363(51).140(42).98(100), (m,4H). l.8l~l.48(m.8H) 55(54).42(65) I 274 -(CH,V 4-F-C 6 H 4 L 7.50~6.98(m,4H).4.80(E) 4.75(.Z)(s, 2H), 3.60-3.15 363(51).140(45).98(96), (m,4H), l.8l-l.46(m,81l) 55(58), 42(100) 275 (CH 2 V 3-CI-C t H 4 7.49-7.18(m, 4H), 4.81(E) 4.74(Z)(s, 2H), 3.62-3.20 379(55).140(52).98(93). (m,4H), I.82~l.50(m,8H) 55(73).42(100) 276 -(CH 2 ) 6 - 4-CI-C 6 H 4 L 7.50-7. l5(m,4H),4.80(.E)4.75(Z)(s.2H), 3.61-3.17 379(56).140(51), 98(82), (in.4H).1.83-1.3(m, 811) 55(70).42(100) 277 -(CH 2 V 3,5-CI 2 -C 6 H, L 7.43-7.16(m, 3H).4.80(E) 4.76(Z)(s.2H).3.63-3.18 413(45), 140(48).98(100), (m.4H), l.86~I.47(m.8H) 42(53) 278 (CH 2 ) 4 - C 4 H,S-2-yl L 7.40~6.94(m, 3H).4.79(E) 4.75(Z)(s, 2H), 3.61-3.13 351(11), 140(50), 98(100), n H (m.4H). l.82~l.43(m.8H) 55(30.42(41) 279 C 2 H, C j H, C 6 H, L 7.50~7.2l(m.5H).4.77(E) 4.64(Z)(s, 2H).3.45(q.411). 319(28), 114(88).86(62), vo vo 1.15(1.611) 72(100) ©δ 280 C 2 H, C,H, 4-CH,-C ( ,H 4 L 7.45~6.98(m, 411), 4.7i(E) 4.65(Z)(s.211), 3.45(q, 411), 333(39), 314(75), 219(100), 2.38(s,3H), 1.10(1,611) 72(82) Table 5 ( Continued ) f 1 1 V 0 R 4 R =CF 3 (0 Comp . No . R 1 R 2 R 3 state(°Q NMR (CDCI,. TMS) δ (ppm) MS (m e) 281 n-C,H, n-C,H, 4-CH,-C t H 4 L 7.46~6.97(m, 4H), 4.7 (E) 4.65(2)(s, 211), 3.21(1, 4H), 361(43). 342(52). 261(100). 2.37(s, 3H), l.98~l .23(m, 4H), 0.91(1. 611) 100(23). 69(58) 282 i-C,H, i C,H 7 4-CH,- ;H 4 73-74 7.45~6.98(m, 4H), 4J8(^ 4.66(Z)(s, 2H). 3.82-3.32 361(52), 342(40), 261(100). (m, 2H). 2.38(s, 3H), 1.38(d, I 2H) 158(49) 283 CH j =CHCH j CH 2 =CHCH 2 C 6 H, L 7.49-7.19(m, 5H), 5.86-5.59(m, 2H), 5.30~5.02(m, 4H), 343( 19), 138(92). 1 10(63). 4.79(^ 4.66(Z)(s, 2H), 4.10-3.62(m, 4H) 55(100) 284 CH 2 =CHCH j CH 2 =CHCH 2 4 CH,-C t H 4 L 7.51 ~6.97(m, 4H), 5.89~5.42(m, 211), 5.39~4.98(m, 411), 357(40), 138(54), 55(100) • l 4.77(E) 4.65(Z)(s, 2H), 4.18~3.48(m, 4H). 2.38(s, 3H) Iv 285 CH 2 =CHCH 2 CH 2 =CHCH 2 3-0^0-0,,^ L 7.51-6.8 l(m, 4H), 6.10-5.5 l(m, 2H), 5.49-4.98(m, 4H), 373(66). 354(23). 138(41 ), 4.79(E) 4.66(Z)(s, 2H), 4.10~3.62(m, 4H), 3.82(s, 3H) 56( 100) 286 CHJ=CHCHJ CH 2 =CHCH 2 3-CF,-C 6 H 4 L 7.89-7.2 l(m, 4H), 5.94~5.42(m. 2H), 5.39-4.96(m, 4H), 41 1(69). 195(100). 138(80). 4.79(E) 4.65(2)(s, 2H).4.18~3.48(m.4H) 1 10(51) 287 CH j =CHCH, CH 2 =CHCH 2 C 4 H,S-2-yI L 7.50-6.9 l(m. 3H). 6.1 l~5.50(m. 2H). 5.50~4.97(m, 4H), 349(13), 183(30), 138( 100), 4.78(E) 4.66(Z)(s, 211), 4 l2-3.6i(m. 4H) 133(48) 288 n-C 4 H, n-C 4 H, 4-CH,-C 6 H 4 L 7.48-6.97(m, 4H).4.79(E) 4.66(2)(s. 2H). 3.2 l (t, 411). 389(42). 370(21), 203( 100). " d O 2.38(s. 3H). 1.82-1.10(m, 811), 0.94(t, 611) H 186(72). 69(48) 289 i C 4 H, i-C 4 H, 4-CH,-C 6 H 4 L 7.45~6.98(m, 411), 4.79(E) 4.65(Z)(s, 2H). 2.83(d. 4H). 389( 14). 170(17), 128(100), vo 2 37(s, 3H). 2.04- 1.37(m. 211), 0.89(d, 1211) 72(34) 290 C 2 H, (CH,) 2 CH C 6 H, 1. 7.7 l~7.28(m, 5H), 4.78(E) 4.-54(Z)(s, 2H), 3.98-3.63 333( 12), 205(40), 128(62), (m, IH), 3. l 2(q. 2H), 1.12(1. 3H). ! .10(d, 6H) 86( 100), 57(71 ) Table 5(Continued) VO VO ϊi R 1 F VO j I R" N γVγ »3 0 R 4 R =CF 3 (") Comp . No . R 1 R 2 R 3' state(°C 1 NMR (CDCl,, TMS) 5 (ppm) MS (m/e) 291 CH, n-C 4 H, 4-CH,-C 6 H 4 L 7.44~6.97(m, 4H), 4.79(E) 4.64(Z)(s, 2H), 3.35(1, 2H), 347(28), 328(16), 203(100), 2.82(s, 3H), 2.28(s, 3H), l.45-l.30(m, H).0.98(1, 3H) 144(67), 69(21) 292 CΛ n-C 4 H, 4 CH,-C H 4 L 7.45~6.96(m, 4H), 4.79(E) 4.65(Z)(s, 2H), 3.40(1, 2H), 361(27), 342(12), 203(100), 3.21(q, 2H), 2.28(s, 3H), 1.46~l.31(m, 4H), 1.10(1, 3H), 158(39), 69(13) 0.97(1, 3H) 293 CH, (C 6 H,)CH 2 C.H, L 7.49~7.01(m, 10H), 4.80(E) 4.66(Z)(s, 211), 4.4l(s, 2H), 367(32), 164(100), 93(54), 2.82(s, 3H) 47(98) 294 CH, (C 6 H,)CH 2 4-CH 3 -C;H 4 L 7.48-6.98(m, 9H), 4.81(E) 4.67(Z)(s, 211).4.43(s, 2H), 381(25), 162(68), 91(100), 2.84(s, 3H), 2.42(s, 3H) 44(28) O H o vo δo - 54 - Herbicidal. Activity Tes Herbicidal activity tests were conducted using test plants planted in screening pots as follows. Each of screening pots, having the shape of a cube and a top surface area of 140 cm 2 , was filled with a wet mixture of paddy soil and a suitable amount of fertilizer, and sowed thereto were 100 barnyardgrass seeds, 20 bulrush seeds, 50 monochoria seeds, 2 flat-sedge tubers and 2 arrow head tubers (see Table 6). Two rice plant seedlings at the 3-leaf stage were then transplanted thereto, followed by filling water to a depth of 3 cm and kept in a greenhouse for 2 days . Added to each of the screening pots thus prepared was 4 ml of a 50% acetone solution containing 0.1% Tween-20 and a predetermined amount of each of the compounds listed in Tables 4 and 5 so that the amount of the compound applied would correspond to 4, 1, 0.25, 0.0625 or 0.015 kg/ha. Then, the pot was kept in a greenhouse for 2 to 3 weeks. The herbicidal activity was determined according to the procedure of Table 7 which was described by Frans et al . , In. research methods in weed science, ed. by Camper, 29-70 (1986) and Cho, K.Y., Search Report by Korea Research Institute of Chemical Technology r 916 (1989))". The results are shown in Table 8. - 55 - Table 6 Abbreviation Genus-species name General name ORYSA Qryza sa iva L. Rice ECHOR Echinochl ra ςjr p-galli Barnyardgrass 8P. BEAUV. var. oryzicola OHWI SCPJU Scirpus iuncoides ROXB Bulrush MOOVA Monochoria vaqinalis Monochoria PRESL CYPSE Cvperus serotinus ROTTB Flat-sedge SAGPY Saσittaria pvσmaea MIO Arrow head Table 7 Score General Rice Weed Description 0 no effect no damage no preventive effect 10 week week a slight damage that can be a slight damage but no 20 medium recovered; no significant preventive effect 30 strong influence on the harvest 40 medium week a visible damage that can a significant preventive 50 medium be recovered but would effect 60 strong reduce the harvest 70 strong week a severe damage that can a practically high I 80 medium not be recovered, and preventive effect, and 90 strong extinction at a score of 80 eradication at a score of s or higher 80 or higher 100 complete total destruction complete eradication O H vo vo δ3 -57 - Table 8 . 1 Comp . 1 . . .1 amount ORYSS ECHOR.SCP,TU MOOVA CYPSE SAGPY No. (kg/ha) 4.0000 90 100 100 100 100 100 1.0000 60 100 100 100 100 50 1 0.2500 10 100 10 90 40 50 0.0625 0 100 0 80 40 20 0.0156 0 60 0 40 10 0 1.0000 90 100 100 100 - 70 0.2500 40 100 70 90 - 60 2 0.0625 0 100 40 90 - 0 0.0156 0 100 20 90 - 0 0.0040 0 75 0 60 - 0 1.0000 80 100 100 100 - 70 0.2500 10 100 90 100 - 50 3 0.0625 0 100 70 B0 - 20 0.0156 0 100 20 60 - 0 0.0040 0 60 0 20 - 0 1.0000 70 100 70 100 100 20 0.2500 10 100 70 100 100 0 4 0.0625 0 100 70 100 .80 0 0.0156 0 100 50 100 0 0 0.0040 0 20 0 0 0 0 1.0000 20 100 100 100 100 60 0.2500 10 100 30 100 100 0 5 0.0625 0 100 0 100 0 0 0.0156 0 95 0 90 0 0 0.0040 0 50 0 10 0 0 1.0000 20 100 100 100 100 60 0.2500 0 100 0 90 100 0 6 0.0625 0 95 0 50 0 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 10 100 100 100 - 30 0.2500 0 100 100 100 - 30 7 0.0625 0 80 30 70 - 10 0.0156 0 60 0 40 - 0 0.0040 0 0 0 0 - 0 1.0000 0 100 20 90 30 70 0.2500 0 100 0 90 30 • 0 8 0.0625 0 95 0 30 -10 0 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 80 100 100 100 0 100 1.0000 50 100 60 100 0 60 9 0.2500 30 100 0 100 0 40 0.0625 0 100 0 100 0 0 0.0156 0 100 0 100 0 0 1.0000 20 100 100 100 100 0 0.2500 10 100 40 70 100 0 10 0.0625 0 100 0 30 10 0 0.0156 0 50 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 60 100 100 100 100 80 1.0000 10 100 100 100 100 50 11 0.2500 0 100 30 90 100 10 0.0625 0 90 10 60 100 0 0.0156 0 1 60 0 0 0 0 - 58- Table 8 (continued) 1 - 1 1 Comp . amount ORYSA ECHOR SCPOT MOOVA CYP.S2 SAGPY No . (kg/ha) i 1.0000 0 100 100 100 100 50 0.2500 0 100 10 90 100 0 12 0.0625 0 100 0 60 10 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 4.O0OO 40 100 70 100 0 100 1.0000 30 100 40 100 0 100 13 0.2500 0 100 0 100 0 100 0.0625 0 95 0 80 0 100 0.0156 0 70 0 40 0 0 1.0000 50 100 100 100 100 70 0.2500 10 100 40 90 100 20 14 0.0625 0 100 20 70 50 0 0.0156 0 80 0 20 0 0 0.0040 0 50 0 0 0 0 1.0000 60 100 100 100 100 100 0.2500 0 100 30 100 100 30 15 0.0625 0 100 0 90 100 20 0.0156 0 90 0 30 20 0 0.0040 0 70 0 0 0 0 1.0000 30 100 100 100 100 50 0.25O0 10 100 50 100 50 0 16 0.0625 0 100 50 100 0 0 0.0156 0 40 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 30 100 20 100 100 20 0.2500 10 100 0 100 100 20 17 0.0625 0 100 0 100 100 20 0.0156 0 90 0 100 40 0 0.0040 0 20 0 0 0 0 4.0000 o 100 30 90 50 20 1.0000 0 100 70 90 0 - 18 0.2500 0 70 40 ω 0 0 0.0625 0 10 0 0 0 0 0.0156 0 0 0 0 0 0 4.0000 50 100 100 100 - 100 1.0000 40 100 100 100 - 100 19 0.2500 40 100 70 100 0 0.0625 20 95 - 100 - 0 0.0156 0 70 0 40 - 0 4.0000 60 100 100 100 100 70 1.0000 30 100 100 100 100 50 20 0.2500 10 100 10 90 30 0 0.0625 0 100 0 .50 20 0 0.0156 0 60 0 30 0 0 1.0000 45 100 80 100 100 10 0.2500 10 100 40 100 100 0 21 0.0625 0 95 10 60 0 0 0.0156 0 60 0 0 0 0 0.0040 0 30 0 0 0 0 4.0000 20 100 50 100 100 0 1.0000 0 100 30 100 100 0 22 0.2500 0 100 30 90 20 0 0.0625 0 100 30 60 0 0 0.0156 0 60 0 40 0 0 - 59 - Table 8 (continued) Comp . amount ORYSA ECHOH SCPvTU MOOVA CYPSE SAGPY No. (kg/ha) 1.0000 30 100 0 90 60 70 0.2500 0 100 0 70 0 0 23 0.0625 0 95 0 50 0 0 0.0156 0 40 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 30 100 40 100 0 0 0.2500 10 100 20 70 0 0 24 0.06.25 0 90 0 50 0 0 0.0156 0 30 0 0 0 0 0.0040 0 10 0 0 0 0 1.0000 10 100 40 100 100 50 0.2500 0 90 0 50 100 0 25 0.0625 0 80 0 0 100 0 0.0156 0 70 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 40 100 50 90 0 0 0.2500 10 100 40 90 0 0 26 0.0625 0 95 30 70 0 0 0.0156 0 70 20 50 0 0 0.0040 0 0 0 20 0 0 1.0000 20 100 20 100 100 10 0.2500 10 100 0 90 50 0 27 0.0625 0 80 0 30 30 0 0.0156 0 10 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 10 100 100 30 0.2500 0 100 0 100 0 0 28 0.0625 0 100 0 100 0 0 0.0156 0 50 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 60 100 100 100 - 100 0.2.500 50 100 100 100 - 60 30 0.0625 40 100 30 90 - 50 0.0156 0 80 10 70 - 0 0.0040 0 50 0 20 - 0 1.0000 40 100 80 100 - 30 0.2500 20 100 50 90 - 0 31 0.0625 0 95 0 80 0 0.0156 0 70 0 50 - 0 0.0040 0 10 0 0 - 0 1.0000 40 100 100 100 - 40 0.2500 30 100 100 100 - 20 32 0.0625 0 90 20 80 - 0 0.0156 0 60 0 20 - 0 0.0040 0 20 0 0 - 0 1.0000 20 100 50 100 - 30 0.2.500 0 100 30 80 - 0 33 0.0625 0 80 0 70 - 0 0.0156 0 40 0 20 - 0 0.0040 0 0 0 0 - 0 - 60 - Table 8 (continued) Comp . " I I I amount ORYSA ECHOR SCP-ruiMOOVA CYPSE SAGPY No . (kg/lia) 1.0000 20 100 100 100 - 20 0.2500 10 100 80 100 - 10 34 0.0625 0 90 10 70 - 10 0.0156 0 70 0 50 - 0 0.0040 0 0 0 0 - 0 1.0000 20 100 100 100 - 50 0.2500 0 100 50 90 - 0 35 0.0625 0 80 30 70 - 0 0.0156 0 50 0 50 - 0 0.0040 0 10 0 20 - 0 1.0000 •40 100 100 100 - 60 0.2500 0 100 20 90 - 60 36 0.06^ 0 90 10 80 - 20 0.01456 0 60 0 50 - 0 0.0040 0 20 0 20 - 0 1.0000 70 100 100 100 - 70 0.2500 20 100 100 100 - 50 37 0.0625 0 100 50 90 - 30 0.0156 0 80 40 80 - 30 0.0040 0 50 20 40 - 0 1.0000 20 100 70 100 - 30 0.2500 10 100 60 100 - 30 38 0.0625 0 80 30 80 - 0 0.0156 0 20 0 40 - 0 0.0040 0 0 0 0 0 1.0000 10 100 70 100 10 0.2500 0 100 10 100 - 0 39 0.0625 0 80 0 70 - 0 0.0156 0 50 0 50 - 0 0.0040 0 50 0 20 - 0 1.0000 0 80 30 100 - 10 0.2.500 0 70 30 100 - 0 40 0.0625 0 30 0 30 - 0 0.0156 0 0 0 30 - 0 0.0040 0 0 0 0 - 0 i.OOOO 0 100 30 100 30 20 0.2.500 0 100 30 100 30 20 42 0.0625 0 80 0 80 • 0 0 0.0156 0 80 0 50 0 0 0.0040 0 10 0 0 0 0 1.0000 0 100 0 90 100 0 0.2.500 0 100 0 80 30 0 43 0.0625 0 95 0 40 10 0 0.0156 0 70 0 20 0 0 0.0040 0 0 0 0 0 0 4.0000 70 100 90 100 100 100 1.0000 60 100 50 100 100 100 44 0.2500 40 100 30 100 100 100 0.0625 20 100 0 70 80 50 0.0156 0 100 0 60 .30 0 - 61 - Table 8 ( continued ) Comp . . 1 1 amount ORYSA ECHOK SCP-JU'MOOVA CYPSE SAGPY No . " "" (.kg/ha) 4.0000 50 100 70 100 100 100 1.0000 40 100 40 100 100 100 45 0.2500 30 100 0 90 100 100 0.0625 20 100 0 60 50 30 0.0156 0 100 0 50 0 0 4.0000 60 100 60 100 90 0 1.0000 20 100 50 100 0 0 46 0.2500 0 100 50 90 0 0 0.0625 0 95 30 70 0 0 0.0156 0 90 0 70 0 0 1.0000 10 100 30 90 90 50 0.2500 0 95 10 70 90 30 47 0.0625 0 80 0 30 0 0 0.0156 0 0 0 0 0 0 0.0040 o 0 0 0 0 0 4.0000 40 100 50 100 100 80 1.0000 30 100 40 90 60 0 48 0.2500 0 100 0 90 0 0 0.0625 0 100 0 50 0 0 0.0156 0 30 0 20 0 0 4.0000 90 100 100 100 0 50 1.0000 40 100 80 100 0 .30 49 0.2500 0 100 70 100 0 0 0.0625 0 100 40 100 0 0 0.0156 0 95 20 50 0 0 1.0000 30 100 70 100 100 20 0.2500 20 100 10 90 100 0 50 0.0625 0 100 0 60 0 0 0.0156 0 95 0 20 0 0 0.0040 0 20 0 0 0 0 1.0000 20 100 30 100 100 0 0.2500 0 100 10 50 100 0 51 0.0625 0 100 0 20 0 0 0.0156 0 20 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 30 100 100 100 - 50 1.0000 20 100 50 100 - • 0 52 0.2500 0 100 0 90 •40 0 0.0625 0 70 0 50 30 0 0.0156 0 70 0 0 30 0 4.0000 20 100 30 100 100 .30 1.0000 10 100 0 90 70 0 53 0.2500 0 100 0 80 50 0 0.0625 0 100 0 80 0 0 0.0156 0 40 0 30 0 0 4.0000 (50 100 100 100 - 20 1.0000 0 100 30 100 - 0 54 0.2500 0 100 20 70 - 0 0.0625 0 100 0 70 - 0 0.0156 0 75 0 0 - 0 4.0000 40 100 T~ioo 100 100 90 1.0000 10 100 0 100 100 40 55 0.2500 0 100 0 80 20 20 0.0625 0 90 0 50 10 0 0.0156 0 60 0 0 0 0 - 62 - Table 8 ( continued) Comp . 1 1 1 amount ORYSA ECHOE SCP4JU'MOOVA.CYPSE SAGPY No. (kg ha) 4.0000 50 100 100 100 100 70 1.0000 10 100 10 100 •100 0 56 0.2500 0 100 10 90 50 0 0.0625 0 100 10 70 0 0 0.0156 0 70 0 20 0 0 4.0000 0 100 0 100 100 0 1.0000 0 100 0 90 40 0 57 0.2500 0 80 0 50 0 0 0.0625 0 50 0 0 0 0 0.0156 0 0 0 0 0 0 4.0000 0 100 0 80 100 100 1.0000 0 100 0 70 100 100 58 0.2500 0 95 0 20 0 0 0.0625 0 60 0 0 0 0 0.0156 0 0 0 0 0 0 1.0000 0 100 20 40 100 10 0.2500 0 100 0 10 50 0 59 0.0625 0 10 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 40 100 0 100 50 60 1.0000 10 100 0 100 50 20 60 0.2500 0 100 0 70 30 0 0.0625 0 90 0 30 0 0 0.0156 0 80 0 0 0 0 4.0000 20 100 40 100 0 0 1.0000 0 100 0 100 0 0 61 0.2500 0 100 0 80 0 0 0.0625 0 100 0 40 0 0 0.0156 0 0 0 0 0 o 4.0000 30 100 100 100 100 80 1.0000 10 100 0 90 60 0 62 0.2500 0 100 0 70 30 0 0.0625 0 80 0 10 0 0 0.0156 0 60 0 0 0 0 4.0000 20 100 0 100 100 0 1.0000 0 100 0 100 80 0 63 0.2500 0 100 0 80 40 0 0.0625 0 100 0 50 0 0 0.0156 0 20 0 0 0 0 4.0000 50 100 0 100 100 30 1.0000 20 100 0 100 100 0 64 0.2500 0 100 0 70 100 0 0.0625 0 70 0 50 0 0 0.0156 0 30 0 30 0 0 4.0000 10 100 30 100 0 30 1.0000 0 100 10 80 0 0 65 0.2500 0 100 0 50 0 0 0.0625 0 60 0 10 0 0 0.0156 0 50 0 0 0 0 4.0000 0 100 30 100 40 0 1.0000 0 100 20 90 40 0 66 0.2500 0 100 0 70 0 0 0.0625 0 95 0 40 0 0 0.0156 0 0 0 0 0 0 - 63 - Table 8 ( continued ) "I Comp. amount 1 1 1 1 ORYSA 1 2CHOR SCPvTO MOOVA CYPSE SAGPY No . (kg/ha) _ι - ■ 4.0000 10 100 40 100 30 70 1.0000 0 100 0 100 20 0 67 0.2500 0 100 0 70 0 0 0.0625 0 60 0 0 0 0 0.0156 0 50 0 0 0 0 4.0000 0 100 40 100 80 20 1.0000 0 100 20 90 0 0 68 0.2500 0 100 0 70 0 0 0.0625 0 60 0 30 0 0 0.0156 0 20 0 0 0 0 4.0000 50 100 0 100 100 30 1.0000 10 100 0 100 20 .20 69 0.2500 0 100 0 100 0 0 0.0625 0 90 0 0 0 0 0.0156 0 90 0 0 0 0 1.0000 20 100 100 100 100 100 0.2500 10 100 20 70 100 0 70 0.0625 0 70 0 10 0 0 0.0156 0 20 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 20 100 50 100 100 50 1.0000 0 100 20 90 100 20 71 0.2500 0 100 0 80 50 0 0.0625 0 100 0 50 0 0 0.0156 0 40 0 0 0 0 1.0000 0 100 30 60 0 70 0.2500 0 95 0 50 0 20 72 0.0625 0 70 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 30 90 50 20 0.2500 0 100 0 60 30 10 73 0.0625 0 70 0 10 0 0 0.0156 0 40 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 0 100 100 70 0.2500 0 100 0 40 50 40 74 0.0625 0 95 0 20 • 0 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 50 90 50 0 0.2500 0 100 30 80 20 0 75 0.0625 0 85 0 40 0 0 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 1 o 100 20 90 100 0 0.2500 1 o 100 0 70 0 0 76 0.0625 0 95 0 40 0 0 0.0156 0 70 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 80 100 30 100 0 20 1.0000 20 100 30 100 0 10 77 0.2500 0 100 0 80 0 0 0.0625 0 95 0 70 0 0 0.0156 0 95 0 40 0 0 - 64 - Table 8 (continued) Comp . amount ORYSA ECHOR . 1 SCPvJU JOOVA CYPSE SAGPY No . (kg/iia) 1.0000 10 100 100 100 100 ι50 0.2500 0 100 30 80 20 0 78 0.0625 0 100 0 70 20 0 0.0156 0 -so 0 20 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 10 100 50 0 0.2500 10 95 0 30 0 0 79 0.0625 0 85 0 30 0 0 0.0156 0 10 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 0 100 100 0 0.2500 0 100 0 0 40 0 80 0.0625 0 100 0 0 0 0 0.0156 0 10 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 30 100 30 100 70 0 0.2500 0 90 30 ,30 0 0 81 0.0625 0 85 20 60 0 0 0.0156 0 50 0 40 0 0 0.0040 0 0 0 20 0 0 1.0000 0 100 20 50 0 0 0.2500 0 100 0 50 0 0 82 0.0625 0 40 0 0 0 0 0.0156 0 40 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 30 0 0 0.2500 0 70 0 0 0 0 83 0.0625 0 20 0 0 0 0 0.0156 0 20 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 0 0 0 0.2500 0 20 0 0 0 0 86 0.0625 0 0 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 10 100 0 0 0 0 0.2.500 0 80 0 0 0 0 87 0.0625 0 20 0 0 • 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 10 100 0 70 .30 0 0.2500 0 100 0 0 0 0 88 0.0625 0 50 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 00 0 0 0 0 - 65 - Table 8 (continued) Comp . amount ORYSA ECHOR SCP,JU|MOOv CYPSE SAGPY No . - (kg/ha) 4.0000 10 100 10 90 0 0 1.0000 0 100 0 50 0 0 89 0.2500 0 100 0 50 0 0 0.0625 0 60 0 0 0 0 0.0156 0 0 0 0 0 0 1.0000 0 100 0 0 0 0 0.2500 0 20 0 0 0 0 90 0.0625 0 0 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 20 90 0 0 0 0 0.2500 0 40 0 0 0 0 91 0.0625 0 10 0 0 0 0 0.0156 0 10 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 0 100 0 0 0.2500 10 100 0 80 0 0 93 0.0625 0 100 0 80 0 0 0.0156 0 80 0 20 0 0 0.0040 0 10 0 0 0 0 1.0000 20 100 0 100 0 40 0.2500 0 100 0 50 0 0 94 0.0625 0 80 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 10 100 0 90 40 0 0.2500 0 100 0 70 30 0 95 0.0625 0 100 0 50 0 0 0.0156 0 0 0 30 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 10 100 50 20 0.2.500 0 95 0 50 0 0 96 0.0625 0 30 0 40 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 30 100 20 80 0 20 0.2.500 20 100 0 30 0 0 97 0.0625 10 90 0 30 • 0 0 0.0156 0 80 0 30 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 90 0 0 0.2500 0 100 0 70 0 0 99 0.0625 0 85 0 50 0 0 0.0156 0 10 0 30 0 0 0.0040 0 0 | 0 0 0 0 - 66 - Table 8 (continued) Comp . amount ORYSA ECHOR SCP.JU KOOVA CYPSE SAGPY No . ~ (kg/ha) 1.0000 20 100 70 100 100 10 0.2500 10 100 0 40 90 0 100 0.06.25 10 100 0 0 0 0 0.0156 10 80 0 0 0 0 0.0040 0 10 0 0 0 0 1.0000 20 100 0 90 100 20 0.2500 0 100 0 80 90 0 101 0.0625 0 95 0 20 0 0 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 10 100 30 90 30 0 0.2500 0 100 10 60 0 0 102 0.0625 0 80 0 0 0 0 0.0156 0 70 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 10 70 0 10 0.2500 0 80 0 40 0 0 103 0.0625 0 10 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 0 100 0 100 30 0 1.0000 0 100 0 100 0 0 106 0.2500 0 100 0 80 0 0 0.0625 0 90 0 0 0 0 1 0.0156 0 50 0 0 0 0 4.0000 20 100 30 90 100 0 1.0000 0 100 30 80 30 0 107 0.2500 0 100 0 70 0 0 0.0625 0 80 0 50 0 0 0.0156 0 30 0 20 0 0 1.0000 0 100 30 90 80 0 0.2500 0 100 0 90 50 0 108 0.0625 0 95 0 70 0 0 0.0156 0 75 0 50 0 0 0.0040 0 0 0 0 0 0 4.0000 20 100 0 100 0 0 1.0000 0 100 0 100 0 ' 0 109 0.2500 0 95 0 30 • 0 0 0.0625 0 90 0 20 0 0 0.0156 0 20 0 0 0 0 1.0000 0 100 50 100 100 0 0.2.500 0 100 10 70 80 0 112 0.0625 0 100 0 40 40 0 0.0156 0 70 0 0 0 0 0.0040 0 0 0 0 0 0 - 67 - Table 8 (continued) Comp . 1 " " " amount ORYSA ECHOR SCPvTO MOOVA' CYPSE SAGPY No. " (lcg/ba) 1.0000 0 100 50 90 0 10 0.2500 0 70 20 70 0 0 113 0.0625 0 40 0 30 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 30 100 0 100 90 0 1.0000 0 100 0 90 0 0 114 0.2500 0 100 0 70 0 0 0.0625 0 90 0 40 0 0 0.0156 0 20 0 0 0 0 1.0000 0 100 20 90 0 0 0.2500 0 95 0 60 0 0 115 0.0625 0 60 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 60 100 30 20 0.2500 0 100 10 60 0 0 116 0.0625 0 85 0 40 0 0 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 10 100 0 0 0.2500 0 100 0 90 0 0 117 0.0625 0 50 0 0 0 0 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 0 100 0 80 100 0 1.0000 0 100 0 40 100 0 118 0.2.500 0 80 0 10 100 0 0.0625 0 50 0 0 40 0 0.0156 0 0 0 0 0 0 4.0000 10 100 20 60 0 0 1.0000 0 100 0 0 0 0 120 0.2500 0 80 0 0 0 0 0.0625 0 60 0 0 0 0 0.0156 0 50 0 0 0 0 4.0000 0 100 100 100 100 50 1.0000 0 100 40 95 100 30 122 0.2500 0 100 0 90 • 100 30 0.0625 0 95 0 70 100 30 0.0156 0 95 0 30 50 30 4.0000 30 100 40 100 100 60 1.0000 20 100 0 100 60 0 123 0.2500 0 100 0 100 0 0 0.0625 0 100 0 80 0 0 0.0156 0 90 0 40 0 0 - 68 - Table 8 (continued) Comp . amount ORYSft ECHOR SCPiTO MOOVA CYPSE SAGPY No . r (kg/hi) 4.0000 40 100 40 100 50 40 1.0000 30 100 40 100 • 0 0 124 0..2500 30 100 30 100 0 0 0.0625 0 80 0 50 0 0 0.0156 0 60 0 20 0 0 4.0000 10 100 50 100 100 100 1.0000 0 100 40 ' 90 100 100 125 0.2500 0 100 0 80 100 0 0.0625 0 60 0 50 0 0 0.0156 0 20 0 .20 0 0 1.0000 0 100 40 100 0 20 0.2500 0 100 20 70 0 10 126 0.0625 0 95 20 60 0 0 0.0156 0 70 0 30 0 0 0.0040 0 0 0 0 o 0 4.0000 30 100 10 100 0 80 1.0000 ϋ 100 0 90 0 0 127 0.2500 0 95 0 50 0 0 0.0625 0 95 0 50 0 0 0.0156 0 50 0 0 0 0 4.0000 0 100 50 100 - - 1.0000 0 100 20 100 0 - 128 0.2500 0 95 0 70 0 - 0.0625 0 95 0 30 0 - 0 0156 0 70 0 0 0 - 1.0000 0 100 10 30 0 0 0.2500 0 30 0 0 0 0 129 0.0625 0 0 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 10 100 0 0 0 0 0.2500 0 90 0 0 0 0 138 0.0625 0 50 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 0 100 0 100 30 80 1.0000 0 100 0 90 30 30 142 0.2500 0 90 0 40 • 20 0 0.0625 0 70 0 20 0 0 0.0156 0 50 0 0 0 0 4.0000 0 100 0 100 60 60 1.0000 0 100 0 90 0 30 143 0.2500 0 100 0 70 0 30 0.0625 0 100 0 50 0 20 1 0.0156 0 0 0 40 0 0 - 69 - Table 8 (continued) Comp . amount 1 ORYSA ECHOR SCPvJU MOOVA CYPSE SAGPY No . (kg/iia) 4.0000 30 100 0 100 . 0 0 1.0000 0 100 0 100 0 0 144 0.2500 0 100 0 30 0 0 0.0625 0 95 0 0 0 0 0.0156 0 30 0 0 0 0 1.0000 0 90 0 70 50 20 0.2500 0 80 0 40 0 0 145 0.0625 0 30 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 70 40 0 0.2500 0 100 0 0 0 0 146 0.0625 0 30 0 0 0 0 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 0 20 30 0.2500 0 30 0 0 0 0 147 0.0625 0 20 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 10 0 20 0.2500 0 50 0 0 0 0 148 0.0625 0 0 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 30 0 30 0 0.2500 0 95 0 0 0 0 151 0.0625 0 20 0 0 0 0 0.0156 0 20 0 0 0 0 0.0040 0 20 0 0 0 0 1.0000 0 100 0 70 0 0 0.2500 0 100 0 70 0 0 152 0.0625 0 50 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 30 20 10 0.2500 0 70 0 0 0 0 153 0.0625 0 0 0 0 • 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 0 60 0 0 0.2500 0 70 0 30 0 0 156 0.0625 0 50 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 o I 0 0 0 0 0 - 70 - Table 8 (continued) l . ,— . T 1 Corπp .i imount ORYSA ECHOR SCP.JU •lOOVA CYPSE SAGPY NO . ; Oce ha) 4.0000 SO 100 100 100 100 1.0000 20 100 100 100 100 162 O2500 0 100 100 100 100 0.0625 0 l∞ 100 80 0 0.0157 4.0000 60 100 70 100 1.0000 40 100 100 100 163 O2500 40 100 100 100 0.0625 10 100 0 70 0.0157 0 95 0 0 4.0000 60 100 100 100 1.0000 50 100 30 100 164 0.2500 20 100 0 100 0.0625 10 100 0 50 0.0157 10 70 0 20 4.0000 100 100 100 100 1.0000 60 100 90 100 165 0.2500 40 100 50 100 0.0625 20 100 50 100 0.0157 0 100 0 30 4.0000 40 100 20 100 1.0000 30 100 0 100 166 0.2500 20 100 0 70 0.0625 0 80 0 50 0.0157 0 ∞ 0 0 4.0000 50 100 100 100 1.0000 50 100 0 100 167 02500 40 100 0 100 0.0625 30 100 0 80 0.0157 20 100 0 60 4.0000 60 100 100 100 100 30 1.0000 20 100 100 100 100 30 168 0.2500 0 100 90 90 70 0 0.0625 0 90 80 90 20 0 0.0157 0 70 0 50 0 0 4.0000 40 100 100 100 100 1.0000 0 100 90 95 100 169 0.2500 0 100 0 90 100 - 0.0625 0 99 0 50 100 0.0157 0 80 0 30 100 4.0000 10 100 0 100 100 1.0000 0 100 0 90 100 170 0.2.500 0 100 0 90 70 0.0625 0 100 0 60 0 0.0157 0 60 0 0 0 4.0000 10 100 100 100 100 1.0000 0 100 100 100 100 171 02500 0 100 70 70 40 0.0625 0 100 50 30 0 0.0157 0 75 0 0 0 71 Table 8 (continued) Comp . am °vin 1 ORYSA ECTOKSCPOT 1 MOOVA 1CYPSE SAGPY N °- (kg ha) 4.0000 50 100 100 100 100 50 1.0000 20 100 60 100 100 30 172 02500 10 100 40 90 50 20 0.0625 0 100 30 80 50 0 0.0157 0 100 30 60 0 0 4.0000 30 100 70 100 100 1.0000 0 100 0 100 100 173 02500 0 100 0 70 0 00625 0 100 0 60 0 0.0157 0 40 0 0 0 4.0000 0 100 10 100 100 1.0000 0 100 0 100 100 1 4 0.2500 0 100 0 70 100 0.0625 0 0 0 20 0 0.0157 0 0 0 0 0 4.0000 40 90 10 100 100 20 1.0000 30 90 0 70 0 10 175 02500 30 50 0 20 0 0 0.0625 10 10 0 0 0 0 0.0157 10 0 0 0 0 0 4.0000 50 100 30 100 1.0000 30 100 0 100 1 6 0.2500 20 100 0 100 0.0625 20 100 0 60 0.0157 1 0 100 0 30 40000 30 100 80 100 100 1.0000 10 100 80 100 100 177 0.2500 10 100 60 100 100 0.0625 0 100 30 70 0 0.0157 0 60 30 0 0 4.0000 30 100 50 100 100 1.0000 0 100 50 100 100 178 0.2500 0 100 30 90 100 0.0625 0 95 30 0 0 0.0157 0 30 0 0 0 4.0000 0 100 30 100 100 1.0000 0 100 30 80 100 179 02500 0 60 0 20 i∞- 0.0625 0 10 0 0 0 0.0157 0 0 0 0 0 4.0000 20 100 30 100 100 1.0000 0 100 20 100 100 180 02.500 0 90 20 50 100 0.0625 0 20 0 0 100 0.0157 0 0 0 0 0 4.0000 10 100 0 100 100 0 1.0000 0 100 0 100 100 0 181 0.2500 0 98 0 90 90 0 0.0625 0 80 0 80 0 0 0.0157 0 60 0 40 0 0 - 72 - Table 8 (continued) imount Comp . 1 1 No. ' ORYSAECHOR SCPvJD MOOVAJCYPSE SAGPY (kg ha) 4.0000 30 100 20 100 70 1.0000 0 100 20 100 183 02500 0 100 10 100 0.0625 0 30 0 0 0 0.0157 0 0 0 0 0 4.0000 10 100 10 100 1.0000 0 100 0 100 185 02500 0 100 0 100 0.0625 0 90 0 0 0.01.57 0 0 0 0 4.0000 10 100 0 95 1.0000 0 100 0 30 186 025. 00 0 100 0 0 0.0625 0 100 0 0 0.0157 0 10 0 0 4.0000 30 100 20 90 1.0000 20 100 0 60 187 02500 10 100 0 0 0.0625 0 80 0 0 0.0157 0 0 0 0 4.0000 80 100 100 100 1.0000 40 100 100 100 189 02500 0 100 100 100 0.0625 0 100 0 100 0.0157 0 100 0 40 4.0000 50 100 100 100 100 1.0000 20 100 100 100 100 190 0.2500 0 100 60 100 100 0.0625 0 100 0 90 100 0.0157 0 100 0 90 0 4.0000 40 100 70 100 100 1.0000 0 100 50 95 100 191 02.500 0 100 30 80 100 0.0625 0 100 0 80 100 0.0157 0 85 0 0 0 4.0000 10 100 60 100 100 1.0000 0 100 50 100 100 192 02.500 0 100 30 100 o • 0.0625 0 80 20 20 0 0.0157 0 30 0 0 0 4.0000 20 100 10 100 1.0000 20 100 0 100 193 0.2500 0 100 0 100 0.0625 0 95 0 30 0.0157 0 10 0 0 - 73 - Table 8 (continued) Comp . amoun r DRYSΛ I; ECHOR SCPvJU MOOVA CYPSEI SAGPY No - (kg/ha) 1 4.0000 20 100 0 100 1.0000 10 100 0 100 194 0.2500 10 70 0 20 • 0.0625 0 30 0 0 0.0157 0 0 0 0 4.0000 40 100 100 100 100 1.0000 20 100 60 100 100 195 02500 20 100 0 70 100 0.0625 0 95 0 0 50 0.0157 0 30 0 0 0 4.0000 40 100 100 100 100 1.0000 30 100 100 100 100 196 0.2500 20 100 20 100 100 0.0625 0 100 10 40 100 0.0157 0 60 0 20 0 4.0000 .50 100 50 100 1.0000 30 100 30 100 197 0.2500 30 100 20 100 0.0625 20 100 0 70 0.0157 0 100 0 50 4.0000 0 100 40 100 100 1.0000 0 100 40 100 100 198 02500 0 100 40 100 0 0.0625 0 60 0 10 0 0.0157 0 30 0 0 0 4.0000 20 100 100 100 100 40 1.0000 0 100 50 100 100 0 199 02.500 0 100 50 100 100 0 0.0625 0 95 30 80 20 0 0.0157 0 60 30 30 0 0 4.0000 0 100 0 100 100 60 1.0000 0 100 0 100 100 0 200 0.2500 0 100 0 90 .50 0 0.0625 0 70 0 ∞ 0 0 0.0157 0 50 0 40 0 0 4.0000 0 100 30 100 100 0 1.0000 0 100 0 100 100 0 201 0.2.500 0 80 0 80 40 - 0 0.0625 0 70 0 60 40 0 0.0157 0 60 0 40 0 0 4.0000 20 100 100 100 100 1.0000 0 100 0 100 100 202 02500 0 80 0 60 100 0.0625 0 60 0 0 0 0.0157 0 0 0 0 0 - 74 - Table 8 (continued) Comp . amoun : " No. i ORYSA ECHOR SCP.TO MOOVA CYPSE SAGPY (kg/ha) 4.0000 30 100 0 100 100 20 1D000 20 100 0 25 5 0 203 02500 10 75 0 .50 0 0 00625 10 30 0 30 0 0 0.0157 0 20 0 0 0 0 4.0000 20 100 40 100 100 20 1D0OO 0 100 40 90 100 10 204 O2500 0 l∞ 30 90 100 10 0O625 0 85 30 70 30 0 0.0157 0 40 0 0 0 0 4.0000 30 100 50 100 100 20 1.0000 30 100 0 95 100 0 205 02500 30 100 0 80 50 0 0.0625 20 80 0 80 0 0 0.0157 10 40 0 20 0 0 4.0000 20 100 40 100 100 30 1.0000 0 100 30 90 100 0 206 0.2500 0 100 10 90 70 0 0.0625 0 100 10 80 0 0 0.0157 0 50 0 0 0 0 4.0000 0 100 20 100 100 30 1.0000 0 100 10 100 100 0 207 0.2500 0 100 0 90 100 0 0.0625 0 80 0 90 0 0 0.0157 0 60 0 50 0 0 4.0000 10 100 20 100 100 20 1.0000 0 100 20 90 30 0 208 02500 0 70 10 80 0 0 0.0625 0 60 0 20 0 0 0.0157 0 0 0 0 0 0 4.0000 0 100 10 100 50 0 1.0000 0 100 10 100 50 0 209 02500 0 70 0 70 50 0 0.0625 0 50 0 40 0 0 0.0157 0 50 0 20 0 0 4.0000 20 100 100 100 1.0000 20 100 100 100 210 02500 10 80 100 95 0.0625 0 0 0 30 0.0157 0 0 0 30 4.0000 0 90 0 0 0 0 1.0000 0 80 0 0 0 0 211 02500 0 70 0 0 0 0 0.0625 0 0 0 0 0 0 0.0157 0 0 0 0 0 0 - 75 - Table 8 (continued) Comp . amount' ORYSA ECHOR SCP-rulMOOVA CYPSE SAGPY No. (kg ha) 4.0000 •40 100 40 100 100 0 1.0000 20 100 40 90 100 0 212 02500 10 100 30 70 70 0 0.0625 0 95 20 20 70 0 0.0157 0 80 0 0 0 0 4.0000 0 100 30 ∞ 30 0 1.0000 0 100 20 70 0 0 213 02500 0 90 10 0 0 0 0.0625 0 60 0 0 0 0 0.0157 0 0 0 0 0 0 4.0000 0 100 iό " 100 0 0 1.0000 0 100 0 90 0 0 214 02500 0 95 0 40 0 0 0.0625 0 70 0 0 0 0 0.0157 0 0 0 0 0 0 4.0000 0 100 40 50 0 0 1.0000 0 100 20 0 0 0 216 02.500 0 60 10 0 0 0 0.0625 0 30 0 0 0 0 0.0157 0 20 0 0 0 0 4.0000 10 100 40 100 0 0 1.0000 0 100 20 80 0 0 218 0.2500 0 100 10 70 0 0 0.0625 0 90 0 30 0 0 0.0157 0 30 o 0 0 0 4.0000 0 100 0 10 0 0 1.0000 0 80 0 0 0 0 219 02500 0 0 0 0 0 0 0.0625 0 0 0 0 0 0 0.0157 0 0 0 0 0 0 4.0000 0 100 3 . 0 100 100 60 1.0000 0 95 0 0 90 0 220 0.2.500 0 60 0 0 0 0 0.0625 0 0 0 0 0 0 0.0157 0 0 0 0 0 0 - 76 - Table 8 ( continued ) Comp . amount SCPJU MOOVA CYPSE SAGPY No . (kg/ha) ORYSA ECHOR 1.0000 80 100 100 100 100 90 0.2500 0 100 100 90 100 80 221 0.0625 0 100 60 90 100 0 0.0156 0 95 20 60 0 0 0.0040 0 20 0 0 0 0 1.0000 80 100 100 100 70 0.2500 70 100 100 100 - 60 222 0.0625 20 100 40 90 - 30 0.0156 0 70 10 80 - 0 0.0040 0 30 0 40 - 0 4.0000 100 100 100 100 100 0 1.0000 60 100 100 100 100 0 223 0.2500 20 100 100 100 0 0 0.0625 0 100 50 .80 0 0 0.0156 0 30 0 30 0 0 1.0000 0 100 100 90 - 50 0.2500 0 100 60 90 - 10 224 0.0625 0 95 10 80 - 0 0.0156 0 40 0 50 - 0 0.0040 0 0 0 0 - 0 1.0000 30 100 100 90 - 50 0.2500 30 100 100 90 80 20 225 0.0625 0 80 20 80 80 0 0.0156 0 60 0 50 70 0 0.0040 0 0 0 20 0 0 1.0000 70 100 100 90 - 60 0.2500 40 100 100 80 90 30 226 0.0625 0 85 30 80 40 0 0.0156 0 50 10 50 0 0 0.0040 0 0 0 20 0 0 4.0000 100 100 100 100 0 100 1.0000 50 100 100 100 0 100 227 0.2500 30 100 100 90 0 100 0.0625 0 100 100 90 0 40 0.0156 0 90 40 70 0 0 1.0000 40 100 100 100 100 60 0.2500 10 100 70 90 100 40 228 0.0625 0 90 0 50 0 10 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 65 100 100 100 - 70 0.2500 0 100 90 90 - 50 229 0.0625 0 80 30 70 - 20 0.0156 0 30 0 40 0 0 0.0040 0 0 0 20 0 0 4.0000 80 100 100 100 100 0 1.0000 60 100 100 100 100 0 230 0.2500 20 100 40 90 100 0 0.0625 20 100 0 80 20 0 0.0156 20 90 0 50 0 0 4.0000 90 100 100 100 100 100 1.0000 90 100 100 100 100 100 231 0.2500 70 100 100 100 100 60 0.6250 0 100 100 100 100 30 0.0156 0 70 40 60 0 0 - 77 - Table 8 ( continued ) Comp . amount SCHOR MOOVA No (kg/ha) ORYSA ECHOR DYPSE SAGPY 1 0000 65 100 100 100 - 50 02500 30 100 100 90 - 50 232 00625 0 100 100 90 - 0 00156 0 90 50 80 50 0 00040 0 70 10 50 0 0 10000 65 100 100 90 - 80 02500 20 100 50 90 60 50 233 00625 0 95 10 70 - 0 00156 0 80 0 70 0 0 00040 0 0 0 20 0 0 1 0000 60 100 100 100 100 70 02500 20 100 100 100 100 50 234 00625 0 100 60 100 100 20 00156 0 80 10 30 0 0 00040 0 30 0 0 0 0 10000 0 100 30 100 100 50 02500 0 100 0 90 20 20 235 00625 0 95 0 80 0 0 00156 0 30 0 10 0 0 OOCWO 0 0 0 0 0 0 40000 60 100 100 100 100 100 1 0000 50 100 100 100 100 100 236 02500 30 100 60 100 0 100 00625 10 80 40 60 0 0 00156 1 0 60 0 40 0 0 1 0000 1 60 100 100 100 100 70 02500 | 10 100 100 100 100 50 237 00625 j 0 100 40 100 100 30 00156 | 0 95 0 80 0 0 00040 | 0 60 0 20 0 0 1 0000 50 100 100 100 100 100 02500 20 100 80 100 90 60 238 00625 0 100 30 60 0 0 00156 0 60 0 20 0 0 00040 0 0 0 0 0 0 40000 100 100 100 100 100 50 1 0000 50 100 100 100 100 30 239 02500 20 100 30 100 100 0 00625 0 90 20 60 20 0 00156 0 20 0 30 0 0 1 0000 10 100 60 100 100 60 02500 0 100 30 90 0 0 2-40 00625 0 90 0 70 0 0 00156 0 60 0 0 0 0 00040 0 0 0 0 0 0 1 0000 10 100 40 90 100 60 02500 0 95 10 90 10 10 241 00625 0 90 0 90 0 0 00156 0 60 0 10 0 0 00040 0 0 0 0 0 0 1 0000 20 100 60 100 100 60 02500 10 100 0 100 80 40 242 00625 0 80 0 40 0 10 00156 0 50 0 10 0 0 00040 j 0 0 0 0 0 0 - 78 - Table 8 ( continued) Comp. amount JU MOOVA SYPSE SAGPY No . (kg/ha) ORYSA ECHOR SCP 1.0000 40 100 100 90 100 50 02.500 10 100 90 90 100 0 243 0.0625 0 100 10 90 0 0 0.0156 0 90 0 30 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 60 100 70 90 02500 0 100 40 50 50 0 244 0.0625 0 100 0 30 40 0 0.0156 0 50 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 100 90 100 0 0.2500 0 100 100 90 100 0 245 0.0625 0 95 30 70 80 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 50 100 100 100 - 60 0.2500 30 100 50 90 - 60 246 0.0625 10 95 0 60 80 30 0.0156 0 40 0 40 - 0 0.0040 0 10 0 20 0 0 1.0000 50 100 100 100 100 80 0.2500 0 100 70 90 100 40 247 0.0625 0 100 40 70 0 10 0.0156 0 80 10 40 0 0 0.0O10 0 60 0 10 0 0 1.0000 70 100 100 100 100 90 0.2500 10 100 100 90 90 40 248 0.0625 0 100 50 90 80 20 0.0156 0 95 20 80 0 0 0.00-40 0 80 0 10 0 0 1.0000 20 100 100 100 100 40 0.2500 10 100 50 100 30 30 249 0.0625 0 100 50 100 0 30 0.0156 0 70 50 50 0 30 0.0040 0 50 50 50 0 0 1.0000 10 100 100 100 100 40 0.2500 0 100 100 100 100 40 250 0.0625 0 80 50 80 100 20 0.0156 0 50 30 50 0 10 0.0040 0 0 0 10 0 0 1.0000 10 100 70 90 100 20 0.2500 0 90 50 90 100 60 251 0.0625 0 60 0 20 0 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 1.0000 20 100 100 100 - 20 0.2500 20 90 70 90 0 0 252 0.0625 10 80 20 80 0 0 0.0156 0 60 0 80 0 0 0.0040 0 0 0 30 0 0 4.0000 70 100 100 100 100 100 1.0000 40 100 100 100 100 90 253 02500 0 100 30 80 100 50 0.0625 0 100 0 70 30 0 0.0156 0 60 0 40 0 0 - 79 - Table 8 ( continued ) Comp . amount NO . ORYSA ECHOR SCPJU (kg/ha) MOOVA CYPSE SAGPY 4.0000 50 100 100 100 100 100 1.0000 40 100 80 100 100 100 254 02.500 20 100 50 90 . 0 0 0.0625 0 95 0 40 0 0 0.0156 0 50 0 0 0 0 1.0000 20 100 50 100 100 60 02500 10 100 20 90 100 0 255 0.0625 0 90 0 70 0 0 0.0156 0 40 0 30 0 0 0.0040 0 40 0 0 0 0 4.0000 60 100 100 100 100 0 1.0000 0 100 50 100 100 0 256 02.500 0 100 0 60 0 0 0.0625 0 80 0 20 0 0 0.0156 0 0 0 0 0 0 1.0000 0 100 40 100 100 0 0.2500 0 100 20 90 100 0 257 0.0625 0 95 0 40 0 0 0.0156 0 40 0 10 0 0 0.00*0 0 0 0 0 0 0 1.0000 10 95 10 90 0 20 02.500 0 80 0 40 0 10 258 0.0625 0 70 0 10 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 4.0000 70 100 100 100 100 90 1.0000 50 100 100 100 100 60 259 0.2500 20 90 40 70 0 0 0.0625 0 80 0 30 0 0 0.0156 0 80 0 0 0 0 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 80 260 02500 50 100 90 100 100 50 0.0625 20 100 40 70 40 0 0.0156 0 60 0 0 0 0 4.0000 100 100 100 100 100 90 1.0000 90 100 100 100 100 0 261 0.2500 20 90 90 60 100 0 0.0625 0 70 30 20 100 0 0.0156 0 0 0 o 0 0 ZOOOO 0 100 0 100 50 50 05000 0 100 0 100 20 0 262 0.1250 0 100 0 90 0 0 0.0310 0 60 0 30 0 0 0.0O80 0 20 0 0 0 0 4.0000 0 100 20 100 100 50 1.0000 0 100 0 100 100 0 263 02500 0 100 0 100 100 0 0.0625 0 95 0 100 50 0 0.0156 0 80 0 30 0 0 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 90 264 0.2500 60 100 100 90 50 80 0.0625 10 100 100 90 30 30 0.0156 0 70 20 70 0 0 - 80 - Table 8 (continued) Comp. amount ORYSA ECHOR SCPiTU MOOVA SYPSE No . SAGPY (kg/ha) 1.0000 50 100 100 100 - 80 02500 10 100 60 90 - 0 265 0.0625 0 95 10 90 . - 0 0.0156 0 80 0 70 - 0 0.0040 0 20 0 60 - 0 1.0000 100 100 100 100 - 90 0.2500 0 100 90 90 - 60 266 0.0625 0 100 20 90 90 20 0.0156 0 70 10 80 0 0 0.0040 0 30 0 60 0 0 1.0000 10 100 50 90 - 80 02500 0 100 40 80 - 0 267 0.0625 0 95 30 80 70 0 0.0156 0 60 0 50 0 0 0.0040 0 0 0 0 0 0 1.0000 40 100 100 90 - 60 0.2500 0 100 90 90 - 40 268 0.0625 0 95 10 80 60 30 0.0156 0 65 0 70 0 0 0.0040 0 20 0 50 0 0 1.0000 70 100 90 100 - 80 0.2500 10 100 30 90 - 50 269 0.0625 0 95 0 80 - 10 0.0156 0 70 0 80 0 0 0.0040 0 0 0 40 0 0 1.0000 90 1 100 100 100 80 02500 50 100 30 90 - 50 270 0.0625 30 100 20 90 - 10 0.0156 10 70 10 80 0 0 0.0040 0 20 10 60 0 0 1.0000 10 100 90 90 - 80 0.2500 0 100 50 80 - 0 271 0.0625 0 90 10 70 60 0 0.0156 0 70 0 60 - 0 0.0040 0 0 0 50 0 0 1.0000 50 100 100 100 100 60 0.2.500 0 100 30 80 20 0 272 0.0625 0 100 0 70 20 0 0.0156 0 70 0 20 0 0 0.0040 0 0 0 0 0 0 1.0000 50 100 100 100 90 0.2500 20 100 100 90 - 70 273 0.0625 0 100 30 90 60 20 0.0156 0 70 20 80 30 0 0.0040 0 30 0 30 30 0 1.0000 60 100 100 100 - 100 0.2500 0 100 100 100 - 90 274 0.0625 0 100 30 90 - 40 0.0156 0 80 30 80 80 0 0.0040 0 60 0 50 0 0 1.0000 20 100 100 100 - 70 0.2500 0 100 50 90 - 50 275 0.0625 0 90 10 80 50 10 0.0156 0 70 0 50 0 0 0.0040 0 0 0 30 0 0 - 81 - Table 8 ( continued ) Comp. amount ORYSA ECHOR SCPJU MOOVA CYPSE SAGPY No . (kg/ha) 1.0000 20 100 70 100 - 70 02500 0 100 30 90 - 20 276 0.0625 0 95 20 80 - 0 0.0156 0 75 0 50 - 0 0.0040 0 20 0 40 0 0 1.0000 20 100 10 100 0 50 0.2.500 0 95 0 90 0 10 277 0.0625 0 30 0 70 0 0 0.0156 0 30 0 ∞ 0 0 0.0040 0 0 0 0 0 0 1.0000 0 100 90 90 50 50 0.2500 0 90 70 90 - 0 278 0.0625 0 75 10 70 - 0 0.0156 0 50 0 ∞ 0 0 0.0040 0 10 0 20 0 0 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 70 279 0.2500 10 100 90 80 100 50 0.0625 0 90 70 70 -10 30 0.0156 0 60 0 30 0 0 4.0000 100 100 100 100 100 60 1.0000 40 100 100 90 100 50 280 0.2500 10 100 100 90 100 0 0.0625 0 1 90 30 30 0 0 0.0156 0 1 20 0 0 0 0 4.0000 40 100 100 100 70 0 1.0000 20 100 100 100 0 0 281 02500 0 90 0 40 0 0 0.0625 0 70 0 0 0 0 0.0156 0 20 0 0 0 0 4.0000 0 100 40 90 0 0 1.0000 0 10O 0 50 0 0 282 0.2500 0 60 0 0 0 0 0.0625 0 40 0 0 0 0 0.0156 0 0 0 0 0 0 4.0000 70 100 100 100 100 0 1.0000 30 100 100 100 100 0 283 0.2500 0 100 50 100 100 0 0.0625 0 90 0 90 100 0 0.0156 0 90 0 20 10 0 4.0000 80 100 100 100 100 0 1.0000 40 100 100 100 100 0 284 0.2500 0 100 0 100 100 0 0.0625 0 80 0 80 100 0 0.0156 0 80 0 0 0 0 4.0000 80 100 100 100 100 100 1.0000 50 100 100 100 100 100 285 0.2500 40 100 90 90 100 100 0.0625 30 100 60 80 60 60 0.0156 0 60 0 50 0 0 4.0000 80 100 100 100 100 0 1.0000 40 100 40 100 100 0 286 0.2.500 20 100 30 90 90 0 0.0625 0 80 20 80 20 0 0.0156 0 60 0 50 10 0 - 82 - Table 8 ( continued ) Comp . amount No . ORYSA ECHOR SCPJϋ MOOVA ■CYPSE SAGPY (kg/ha) 4.0000 60 100 100 100 100 100 1.0000 40 100 80 100 100 100 287 02500 30 100 40 100 50 100 0.0625 0 80 30 100 30 100 0.0156 0 80 0 60 30 50 4.0000 50 100 40 90 50 0 1.0000 0 100 0 40 0 0 288 &2500 0 90 0 0 0 0 0.0625 0 50 0 0 0 0 0.0156 0 10 0 0 0 0 4.0000 0 80 0 40 100 60 1.0000 289 0.2500 0.0625 0.0156 40000 100 100 100 100 100 80 1.0000 40 100 100 100 100 80 290 0.2500 10 100 100 100 100 50 0.0625 0 100 50 70 40 0 0.0156 0 70 0 20 0 0 4.0000 100 100 100 100 100 0 1.0000 40 100 100 100 100 0 291 0.2500 10 100 0 100 100 0 0.0625 0 100 0 80 100 0 00156 0 80 0 0 0 0 40000 60 100 100 100 100 0 1.0000 30 100 100 100 100 0 292 0.2500 0 100 0 50 0 0 00625 0 95 0 0 0 0 0.0156 0 20 0 0 0 0 40000 70 100 100 100 100 90 1.0000 0 100 100 100 30 90 293 0.2500 0 100 100 100 30 0 0.0625 0 100 0 80 20 0 00156 0 50 0 1 20 0 0 40000 50 100 90 1 100 100 40 1 0000 20 100 60 100 20 - 294 0.2500 0 100 30 80 0 - 0.0625 0 80 0 80 0 0 00156 0 0 ° 70 0 0 - 83 - As can be seen from Table 8, the compounds of the present invention have high herbicidal activity against a wide spectrum of weeds and are very selective, e.g., they do not harm rice plants. While the invention has been described with respect to the specific embodiments, it should be recognized that various modifications and changes may be made by those skilled in the art to the invention which also fall within the scope of the invention as defined by the appended claims .

Claims: - 84 - What is claimed is: 1. A compound of formula (I): 0 R 1 R N-C-CH 2 0-CF=CR R /i (I) wherein: R 1 is a phenyl group optionally having one or more substituents selected from the group consisting of C 1-6 alkyl, halogen-substituted C,_ 6 alkyl, C,_ 6 alkoxy and halogen; R 2 is a C 1-6 alkyl group; or R 1 and R 2 together with the nitrogen atom to which they are bound form a 5-, 6- or 7-membered nitrogen heterocycle optionally having one or more ring oxygen atoms, double bonds and C 1 _ 6 alkyl substituents; R 3 is a phenyl or thiophen-2-yl group optionally having one or more substituents selected from the group consisting of C-_ 6 alkyl, halogen-substituted C 1 _ 6 alkyl, C 1-6 alkoxy, methylenedioxy and halogen; and R 4 is a perfluoro C 1-6 alkyl group. 2. The compound of claim 1, which is the E isomer of formula ( I-a) : (I-a) - 85 - 3. The compound of claim 1, which is the Z. isomer of formula (I-b) : R F (I-b) O R 4. The compound of claim 1, wherein R 1 is phenyl group optionally having a halogen, methyl or methoxy substituent; R 2 is a methyl or i-propyl group; R 3 is a phenyl group optionally having a halogen or methoxy substituent; and R A is CF 3 or CF 2 CF 3 . 5. The compound of claim 1, wherein R 1 and R 2 together with the nitrogen atom to which they are bound form a piperidino, hexamethyleneimino, morphorino or 1,2,3,6- tetrahydropyridino ring optionally having one or two C 1-2 alkyl substituents, R 3 is a phenyl group optionally substituted with a halogen or methoxy group and R 4 is CF 3 . 6. A process for the preparation of the compound of claim 1 which comprises reacting a compound of formula (II) with a compound of formula (III) in the presence of a base: R 1 R 2 - N γ^OH (i i) O F F R (in) R 4 wherein R, R 2 , R 3 and R 4 have the same meanings as defined in claim 1. - 86 - 7. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 1 as an active ingredient and an inert carrier.

Inventors: HONG KYUNG SIK, KIM BUM TAE, KWON YONG WOONG, PARK JAE EUP, PARK NO KYUN, HONG, KYUNG, SIK, KIM, BUM, TAE, KWON, YONG, WOONG, PARK, JAE, EUP, PARK, NO, KYUN
Applicants: HONG KYUNG SIK, KIM BUM TAE, KOREA RES INST CHEM TECH, KWON YONG WOONG, PARK JAE EUP, PARK NO KYUN, HONG, KYUNG, SIK, KIM, BUM, TAE, KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY, KWON, YONG, WOONG, PARK, JAE, EUP, PARK, NO, KYUN
Application year: 1999
Main classification: C07C235
IPC codes: A01N37, A01N43, C07C235, C07D203, C07D211, C07D215, C07D295, C07D317, C07D333, C07D409