Abstract:
The present invention relates to 1,2,4-oxadiazole derivative of the formula (I) ##STR1## wherein X represents a chlorine or fluorine atom or methyl group, 
     Y represents a chlorine or fluorine atom, 
     n is an integer of 1 or 3. 
     The compounds of the invention have a extremely high selectively between paddy rice or crop plants and weeds, and a strong activity on various weeds. Moreover, the compounds have a very low phytotoxicity to paddy rice and crop plants.

Description:
This application is a continuation of Ser. No. 07/373,807, filed Jun. 29, 1989, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to novel 1,2,4-oxadiazole derivatives having an excellent herbicidal activity, methods of preparation therefore and the herbicidal composition comprising it. 
     2. Description of the Invention 
     Phenoxy type herbicides such as 2,4-D, 2,4,5-T, MCPA and MCPB have been employed as post-emergence application to control paddy and upland weeds. Since the phenoxy type herbicides cause the severe phytotoxicity to paddy rice and crop pants depending on the timing of application or the weather conditions, it has been strongly desired to develop a new type of herbicide which is able to overcome the phytotoxicity on paddy rice and crop plants and control annual and perennial weeds in paddy and upland field. In other words, a new type of herbicide should have an extremely high selectivity between paddy rice or crop plants and weeds and a strong activity on weeds. 
     SUMMARY OF THE INVENTION 
     Under the above circumstances, the present inventors conducted intensive studies for developing herbicides having low phytotoxicity to paddy rice and crop plants and high selectively between paddy rice or crop plants and weeds. They found that 1,2,4-oxadiazole derivative of the following formula(I) has low phytotoxicity, high selectivity and strong activity. 
     Accordingly, it is an object of the invention to provide a new type of herbicide which can industrially be produced and which is able to control annual and perennial weed in paddy and upland field with keeping high selectivity between crops and weeds. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention relates to 1,2,4-oxadiazole derivative of the formula(I) ##STR2## wherein X represents a chlorine or fluorine atom or methyl group, 
     Y represents a chlorine or fluorine atom, 
     n is an integer of 1 or 3, and 
     R represents a C 3-7  alkyl group; a benzyl group substituted by bromine atom, chlorine atom, fluorine atom, C 1-2  alkyl, nitro, amino, acetylamino, thioethoxycarbonylamino, diethylcarbamyl or dimethoxy group; a phenoxymethyl group substituted by chlorine atom or fluorine atom; a methyl group substituted by bromine atom, chlorine atom, fluorine atom, hydroxy, acetate, haloacetate, C 1-2  alkylcarbamate, phenoxybenzoate, methylsulfonate, phenoxyacetate, ethyloxalate, C 1-3  alkylamino, fluorophenylamino, phthalimide, phenylsulfonylamino, pyrrolidine, thiophenoxy, ethyldithiophosphonate, phenylsulfonyl, diethylthiocarbamate, aminocarbamyl or ethoxycarbonyl group; a phenyl group substituted by chlorine atom, fluorine atom, methoxy or fluoromethyl group; a C 2-3  alkoxy or phenoxy group unsubstituted or substituted by chlorine atom, fluorine atom or C 2  alkoxy group; an amino group unsubstituted or substituted by C 5  alkyl, acetyl, C 1-2  alkoxycarbonyl, methylcarbamyl, phenylsulfonyl; a bromine or chlorine atom; a carbonyl group substituted by C 1-4  alkylamino, C 1-2  alkoxy, amino, azido, halophenylamino, acetylamino, methylsulfonylamino, C 1-4  alkyl, benzyl or phenyl group; an oxime group substituted by C 1-4  alkyl or phenyl group; or an imine group substituted by C 1-2  alkoxy, amino, hydroxyamino, ethylphosphonyl or chlorine atom. 
     The compounds of formula(I) of this invention can be prepared, for example, by the following processes: 
     (1) Method 1 ##STR3## wherein X represents chlorine atom or methyl group, 
     Y represents chlorine atom, 
     n is an integer of 1 or 3, and 
     R represents C 3-7  alkyl group; a substituted benzyl group; a halomethyl group; a substituted phenoxymethyl group; a substituted phenyl group; a C 2-3  alkoxy or substituted phenoxy group; an ester group; or an ester methyl group. 
     In other words, the compound(I) of this invention can be prepared by reacting the compound(II) with acylchloride of the compound(III). 
     The above reaction is carried out at reflux temperature in the presence of a catalyst for 1 to 5 hours. Various solvents can be used in this invention, which include acetone, alcohol, dioxane, etc. For the catalyst, dimethylamine, trimethylamine, boron trifluoride etherate, sodium methoxide, etc. may be used. 
     (2) Method 2 ##STR4## wherein, X represents chlorine atom or methyl group, 
     Y represents chlorine atom, 
     n is an integer of 1 or 3, 
     M represents hydrogen or sodium atom, 
     Z is nitrogen, oxygen or sulfur atom, and 
     if Z is a nitrogen atom, R 1  or R 2  is a C 1-2  alkyl group, hydrogen atom, a substituted phenyl group, an aryl sulfonyl group or a cyclized acyl group; and 
     if Z is oxygen or sulfur atom, R 1  is a phenyl group or a substituted carbonyl group. 
     The above reaction is carried out at reflux temperature in the presence of base. Various solvents can be used in this reaction, which include acetone, dioxane, toluene or xylene, tetrahydrofuran, acetonitrile, etc. For the base, they may be employed pyridine, triethylamine, potassium carbonate, sodium hydride, etc. 
     (3) Method 3 ##STR5## wherein X represents chlorine atom or methyl group, 
     Y represents chlorine atom, 
     n is an integer of 1 or 3, and 
     each of R 1  and R 2 , which may be same or different, represents a hydrogen atom, C 1-4  alkyl group, an acyl group, a sulfonyl group, an unsubstituted or substituted phenyl group, an amino group or a methoxy group. 
     The above reaction is carried out at room temperature in the organic solvent for 30 minutes to 1 hour. For the solvent, alcohol such as methanol, ethanol and isopropanol, acetone, acetonitrile, tetrahydrofuran, etc. can be used. 
     (4) Method 4 ##STR6## wherein X and Y represent chlorine atoms, 
     R represents C 1-4  alkyl group, a benzyl group or phenyl group. 
     The above reaction is proceeded for 1 to 2 hours at -78° C. in the organic solvent. For the solvent, tetrahydrofuran, diethyl ether can be used. 
     (5) Method 5 ##STR7## wherein X and Y represent chlorine atoms, 
     R represents C 1-4  alkyl group or a phenyl group and 
     R 2  represents a hydrogen atom or C 2-3  alkyl group. 
     The above reaction is carried out at reflux temperature in the presence of the organic solvent. For the solvent, alcohol such as methanol, ethanol and isopropanol, acetone, acetonitrile, tetrahydrofuran, etc. can be used. 
     (6) Method 6 ##STR8## wherein, X and Y represent chlorine atoms and 
     R 1  represents C 1-3  alkyl group unsubstituted or substituted by methoxy group. 
     The above reaction is carried out at reflux temperature in the presence of the organic solvent. For the solvent, isopropyl alcohol can be used. 
     (7) Method 7 ##STR9## wherein, X and Y are chlorine atoms, 
     Z is a nitrogen or oxygen atom, and 
     if Z is a nitrogen atom, R 1  or R 2  is a hydrogen atom or C 1-2  alkyl group; and if Z is an oxygen atom, R 1  is C 1-3  alkyl group. 
     The above reaction process is carried out a reflux temperature in the presence of the organic solvent for 1 hour and subsequently at room temperature for 15 hours. For the solvent, alcohol such as methanol, ethanol and propanol can be used in order to prepare carbamate group. However, the reaction should be furthermore carried out for 1 to 4 hours at reflux temperature in the presence of dioxane as a solvent to prepare urea group. 
     (8) Method 8 ##STR10## wherein X and Y are chlorine atoms, and 
     R represents C 1-2  alkyl group. 
     The above reaction process is carried out at room temperature in the presence of the organic solvent for 3 to 4 hours. For the solvent, alcohol such as methanol or ethanol can be used. 
     (9) Method 9 ##STR11## wherein X and Y represent chlorine atoms, 
     R 1  represents C 1-2  alkyl group, and 
     R 2  represents a hydrogen atom or hydroxy group. 
     The above reaction is carried out at room temperature in the presence of the organic solvent for 24 hours. For the solvent, alcohol such as methanol or ethanol can be used. 
     After the reaction is completed, the final product can be separated and/or purified by the conventional methods, if necessary. For instance, the reaction mixture is washed with water, followed by distillation of the solvent, and the residue being purified by column chromatography to obtain the compound(I) with a high yield. 
    
    
     Other features of the invention will become apparent in the course of the following description of the exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof. 
     EXAMPLES 
     Example 1 
     3-n-propyl-5[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole. Compound No. 1 
     1.02 g of butylamidoxime, 2.40 g of 2,4-dichlorophenoxyacetyl chloride and 0.14 g of borontrifluoride etherate were added to 50 ml of toluene. The mixture was heated to reflux for 6 hours. After completion of reaction, the mixture was washed with 100 ml water and then subjected to distillation of toluene, and the residue was purified by column chromatography using a mixture of solvent(benzene:ether=4:1) to obtain 1 g of the desired compound(yield: 69.7%). 
     Example 2 
     3-allyl-5-[(2-chloro-4-fluorophenoxy)methyl]-1,2,4-oxadiazole: Compound No. 145 
     0.71 g of 2-chloro-4-fluorophenol, 0.77 g of 3-allyl-5-chloromethyl-1,2,4-oxadiazole and 0.83 of potassium carbonate were added to 20 ml of acetone. After completion of the reaction, the resulting precipitates were filtered out from the mixture and then acetone was removed by distillation, and the residue was purified by column chromatography (benzene:hexane=1:1) to obtain 1.05 g of the desired product(yield: 80.8%). 
     Example 3 
     3-diethylcarbamyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadizaole: Compound No. 99 
     1.58 g of 3-ethoxycarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole and 0.73 g of diethylamine were added to 30 ml of methanol. The mixture was stirred at room temperature for 1 hour. The resulting precipitates were filtered out from the reaction mixture and then washed with 50 ml of methanol. Upon drying the white solid, 1.46 g of the desired product (yield: 84.9%) was obtained. 
     Example 4 
     3-ethylcarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole: Compound No. 112 
     0.95 g of 3-ethoxycarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole was added to 30 ml of tetrahydrofuran. The mixture was cooled to -78° C., and then 3 ml of ethylmagnesium bromide (2M solution) was added dropwise. After the mixture was stirred at -78° C. for 1 hour, it was poured into cold aqueous 5% HCl solution. After the resulted product was extracted with ether and concentrated, it was purified by column chromatography(hexane:ethylacetate=4:1) to obtain 0.75 g of the desired product(yield: 83.0%). 
     Example 5 
     3-(alpha-hydroxyiminopropyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole: Compound No. 119 
     0.9 g of 3-ethylcarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole and 0.21 g of hydroxyamine hydrochloride were added to 10 ml of methanol. The mixture was heated to reflux for 4 hours. After evaporation of methanol, water was added to the residue. The aqueous solution was extracted with ethylacetate. After evaporation of ethylacetate, the residue was purified by column chromatography(benzene:ether=1.1) to provide 0.80 g of the desired product(yield: 85.0%). 
     Example 6 
     3-(1-hydroxybutyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole: Compound No. 138 
     0.316 g of 3-propylcarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole and 0.20 g of aluminum isopropoxide were added to 10 ml of isopropanol. The mixture was heated to reflux for 48 hours. After evaporation of isopropanol, water was added to the residue. The aqueous solution was extracted with ethylacetate. After evaporation of ethylacetate, the residue was purified by column chromatography(hexane: ethylacetate=3:2) to provide 0.17 g of the desired product(yield: 54.0%). 
     Example 7 
     3-N,N-dimethylureido-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole: Compound No. 80 
     1.57 g of 3-azidocarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole was added to 20 ml of dioxane. After the mixture was refluxed for 1 hour, 0.30 g of dimethylamine was added with formation of bubble and then the mixture was stirred at room temperature for 15 hours. The resulting precipitates were filtered from the mixture and washed with dioxane. Upon drying the precipitates, 0.9 g of the desired product was obtained (yield: 55.0%). 
     Example 8 
     3-(iminomethoxymethyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole: Compound No. 125 
     2.17 g of 3-(trichloromethyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole was added to 50 ml of methanol. An excess of ammonia gas was added with formation of bubble at 0° C. and then the mixture was stirred at room temperature for 4 hours. After evaporation of methanol, water was added to the residue. The aqueous solution was extracted with ethylacetate. After evaporation of ethylacetate, the residue was purified by column chromatography(hexane:ethylacetate) to provide 0.92 g of the desired product(yield: 50.9%). 
     Example 19 
     3-iminoaminomethyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole: Compound No. 128 
     0.62 g of 3-iminomethoxymethyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole was added to 20 ml of methanol. An excess of ammonia gas was added with formation of bubble at 0° C. and then the mixture was stirred at room temperature for 24 hours. The resulting white precipitates were filtered from the reaction mixture and then washed with methanol. Upon drying the white precipitates, 0.54 g of the desired product was obtained(yield: 94.4%). 
     The typical compounds prepared by the similar method to the above examples are shown in Table 1 together with their physical properties. 
     
         TABLE 1  ##STR12## Element analysis (%)  Compound  Physical Calculated value (Measured value) No. R n X Y properties C H N NMR (δ, ppm)   1 CH.sub.3 CH.sub.2 CH.sub.2 1 Cl Cl mp 39-40° C. 50.19 4.21 9.75 7.25-6.80(m, 3H), 5.15(s, 2H),       (50.33) (4.28) (9.57) 2.72(5, 2H), 1.92-1.52(m, 2H),          0.98(t, 3H) 2 (CH.sub.3).sub.2 CH 1 Cl Cl oil 50.19 4.21 9.75 7.20-6.80(m, 3H), 5.20(s, 2H),       (50.08) (4.18) (9.83) 3.24-2.87(m, 1H), 1.30(d, 6H) 3 (CH.sub.3).sub.3 C 1 Cl Cl mp 33-34°  C. 51.85 4.69 9.30 7.30-6.80(m, 3H), 5.25(s, 2H),  (51.90) (4.65) (9.22) 1.35(s, 9H) 4 CH.sub.2CHCH.sub.2 1 Cl Cl oil 50.55 3.54 9.82 7.40-6.80(m, 3H), 6.30-5.70       (50.58) (3.49) (9.78) (m, 1H), 5.35-5.10(m, 4H),          3.65-3.45(m, 2H)  5 ##STR13##  1 Cl Cl mp 40-41°  C. 56.65(56.60) 4.76(4.83) 8.26(8.28) 7.25-6.85(m, 3H), 5.40(m, 1H),5.20(s, 2H), 3.25(s, 2H), 2.10-1.85(m, 4H), 1.75-1.42(m, 4H)  6  ##STR14##  1 Cl Cl oil 54.41(54.25) 3.12(3.18) 7.93(7.80) 7.27-6.65(m, 7H), 5.10(s, 2H),3.90(s, 2H)  7 ##STR15##  1 Cl Cl mp 65-66°  C. 46.41(46.47) 2.68(2.70) 6.76(6.67) 7.30-6.65(m, 7H), 5.02(s, 2H),3.80(s, 2H)  8 ##STR16##  1 Cl Cl mp 75-76°  C. 49.58(49.62) 2.60(2.65) 7.23(7.17) 7.30-6.70(m, 6H), 5.30(s, 2H),4.20(s, 2H)  9 ##STR17##  1 Cl Cl mp 42-43°  C. 58.47(58.42) 4.04(4.09) 8.02(8.11) 7.10-6.80(m, 7H), 5.00(s, 2H),4.10(s, 2H), 2.20(s, 3H)  10 ##STR18##  1 Cl Cl mp 33-34°  C. 59.52(59.60) 4.44(4.51) 7.71(7.59) 7.30-6.70(m, 7H), 5.10(s, 2H),3.95(s, 2H), 2.50(q, 2H),1.18(t, 3H)  11 ##STR19##  1 Cl Cl oil 50.64(50.73) 2.75(2.71) 6.95(6.92) 7.50-6.70(m, 7H), 5.15(s, 2H),4.10(s, 2H)  12 ##STR20##  1 Cl Cl mp 87-88°  C. 53.85(53.78) 3.19(3.22) 7.39(7.43) 7.30-6.70(m, 6H), 5.80(s, 2H),5.25(s, 2H), 3.90(s, 2H)  13 ##STR21##  1 Cl Cl mp 68-69° C. 50.55(50.50) 2.92(2.91) 11.05(11.08) 8.00-6.80(m, 7H), 5.20(s, 2H),4.05(s, 2H)  14 ##STR22##  1 Cl Cl mp 95-95° C. 54.88(54.82) 3.74(3.69) 12.00(12.09) 7.20-6.40(m, 7H), 5.20(s, 2H),4.00(bs, 2H), 3.88(s, 2H)  15 ##STR23##  1 Cl Cl mp 87-88° C. 55.12(55.16) 3.85(3.88) 10.71(10.68) 7.50-6.95(m, 7H), 5.15(s, 2H),4.20(s, 2H), 3.10(bs, 1H),1.95(s, 3H)  16  ##STR24##  1 Cl Cl mp 80-81°  C. 52.06(51.98) 3.91(3.87) 9.59(9.64) 7.50-6.90(m, 7H), 5.20(s, 2H),3.95(s, 2H), 2.98-2.80(m, 3H),1.33(t, 3H)  17 ##STR25##  1 Cl Cl oil 58.07(58.15) 4.87(4.80) 9.67(9.63) 7.30-6.60(m, 7H), 5.20(s, 2H),4.00(s, 2H), 3.35(q, 4H),1.28(t, 6H)  18 ##STR26##  1 Cl Cl oil 49.28(49.38) 2.95(3.01) 8.21(8.09) 7.30-6.60(m, 6H), 5.20(s, 2H),4.20(s, 2H)  19 FCH.sub.2 1 Cl Cl mp 63-64° C. 43.33 2.53 10.11 7.38-6.73(m, 3H), 5.47(d, 2H),       (43.28) (2.58) (10.04) 5.32(s, 2H) 20 ClCH.sub.2 1 Cl Cl mp 65-66°  C. 40.92 2.4) 9.54 7.30-6.80(m, 3H), 5.25(s, 2H),       (40.97) (2.48) (9.47) 4.55(s, 2H) 21 BrCH.sub.2 1 Cl Cl oil 35.51 2.07 8.29 7.45-6.81(m, 3H), 5.32(s, 2H),  (35.45) (2.01) (8.35) 4.42(s, 2H) 22 HOCH.sub.2 1 Cl Cl mp 76-77° C. 43.70 2.91 10.19 7.48-6.79(m, 3H), 5.38(s, 2H), (43.83) (2.87) (10.24) 4.73(s, 2H), 3.82(bs, 1H)  23 ##STR27##  1 Cl Cl oil 52.04(51.98) 2.98(2.93) 7.59(7.55) 7.32-6.62(m, 7H), 5.38(s, 2H),5.22(s, 2H)  24 ##STR28##  1 Cl Cl mp 78-79°  C. 47.60(47.68) 2.48(2.41) 6.94(6.99) 7.34-6.54(m, 6H), 5.43(s, 2H),5.23(s, 2H)  25 ##STR29##  1 Cl Cl mp 54-55° C. 49.63 (49.55) 2.58(2.63) 7.24(7.21) 7.34-6.56(m, 6H), 5.43(s, 2H),5.22(s, 2H)  26 ##STR30##  1 Cl Cl oil 50.67(50.83) 2.90(2.79) 7.39(7.30) 7.30-6.71(m, 7H), 5.21(s, 2H),5.11(s, 2H)  27 ##STR31##  1 Cl Cl mp 57-59°  C. 47.60(47.42) 2.48(2.57) 6.94(6.99) 7.34-6.71(m, 7H), 5.20(s, 2H),5.12(s, 2H)  28 ##STR32##  1 Cl Cl mp 87-88°  C. 49.82(49.97) 2.85(2.88) 7.27(7.32) 7.32-6.62(m, 7H), 5.44(s, 2H),5.24(s, 2H)  29 ##STR33##  1 Cl Cl oil 46.00(46.19) 3.86(3.81) 10.72(10.79) 7.70-6.30(m, 6H), 5.40(s, 2H), 5.22(s, 2H)  30 ##STR34##  1 Cl Cl mp 52-53°  C. 45.44(45.37) 3.16(3.09) 8.84(8.89) 7.31-6.79(m, 3H), 5.28(s, 2H),5.19(s, 3H), 2.21(s, 3H)  31 ##STR35##  1 Cl Cl mp 61-62° C. 45.10(45.24) 3.76(3.72) 12.14(12.19) 7.31-7.12(m, 3H), 6.38(bs, 1H),5.38(s, 2H), 5.12(s, 2H),3.24(q, 2H), 1.23(t, 3H)  32 ##STR36##  1 Cl Cl oil 53.50(53.37) 2.91(2.94) 8.14(8.11) 8.23-6.89(m, 11H), 5.50(s, 2H),5.48(s, 2H)  33 ##STR37##  1 Cl Cl mp 118-119° C. 45.10(45.25) 3.76(3.79) 12.14(12.09) 7.52-7.23(m, 3H), 5.62(s, 2H),5.15(s, 2H), 2.98(s, 6H)  34 ##STR38##  1 Cl Cl mp 69-70°  C. 37.40(37.48) 2.83(2.86) 7.93(7.88) 7.32-6.75(m, 3H), 5.22(s, 2H),5.20(s, 2H), 3.12(s, 3H)  35 ##STR39##  1 Cl Cl mp 54-55°  C. 40.98(40.83) 2.56(2.57) 7.97(7.92) 7.38-6.75(m, 3H), 5.43(s, 2H),5.42(s, 2H), 4.82(s, 2H)  36 ##STR40##  1 Cl Cl oil 37.33(37.28) 2.07(2.11) 7.26(7.29) 7.32-6.83(m, 3H), 5.98(s, 1H),5.43(s, 2H), 5.12(s, 2H)  37 ##STR41##  1 Cl Cl oil 44.81(44.97) 3.20(3.26) 7.47(7.51) 7.32-6.75(m, 3H), 5.43(s, 2H),5.21(s, 2H), 4.21(q, 2H),1.23(t, 3H)  38 ##STR42##  1 Cl Cl oil 45.25(43.49) 2.51(2.48) 5.86(5.92) 7.64-6.23(m, 6H), 5.31(s, 2H),5.30(s, 2H), 4.78(s, 2H),  39 ##STR43##  1 Cl Cl mp 99-101° C. 41.01(40.88) 3.15(3.08) 11.04(11.10) 7.42-6.81(m, 3H), 6.12(bs, 1H),5.21(s, 2H), 5.20(s, 2H), 3.42(t, 4H)  40 CH.sub.3 NHCH.sub.2 1 Cl Cl mp 133-134° C. 45.85 3.85 14.58 7.30-6.70(m, 3H), 5.20(s, 2H),       (45.98) (3.79) (14.64) 3.85(s, 2H), 2.45(s, 3H),          2.20(bs, 1H) 41 CH.sub.3 CH.sub.2 NHCH.sub.2 1 Cl Cl oil 47.70 4.34 13.91 7.30-6.70(m, 3H), 5.20(s, 2H),       (47.98) (4.38) (13.83) 3.85(s, 2H), 2.60(q, 2H),          2.10(bs, 1H), 1.15(t, 3H) 42 (CH.sub.3 CH.sub.2).sub.2 NCH.sub.2 1 Cl Cl oil 50.92 5.19 12.73 7.30-6.70(m, 3H), 5.20(s, 2H),       (50.85) (5.22) (12.78) 3.85(s, 2H), 2.68(q, 4H),          1.05(t, 6H)  43 ##STR44##  1 Cl Cl oil 52.19(52.04) 3.26(3.19) 11.42(11.70) 7.30-6.40(m, 7H), 5.20(s, 2H),4.37(s, 2H), 3.37(bs, 1H),  44 ##STR45##  1 Cl Cl mp 98-99° C. 49.14(49.29) 3.83(3.89) 12.28(12.34) 7.41-6.80(m, 3H), 5.20(s, 2H),4.65(s, 2H), 3.33(t, 2H),2.50-2.05(m, 4H) 45  ##STR46##  1 Cl Cl oil 53.70(53.85) 3.98(3.91) 11.05(11.12) 7.80-6.74(m, 8H), 5.20(s, 2H),4.52(s, 2H), 2.95(s, 3H)  46 ##STR47##  1 Cl Cl oil 46.50(46.54) 3.70(3.78) 8.56 (8.61) 7.62-6.85(m, 7H), 5.21(s, 2H),4.50(s, 2H), 3.36(t, 2H),1.80-1.62(m, 2H), 1.16(t, 3H)  47  ##STR48##  1 Cl Cl oil 52.96(52.89) 3.70(3.74) 10.29(10.33) 7.32-6.85(m, 3H), 6.81(m, 2H),5.23(s, 2H), 4.70(s, 2H),3.18(m, 2H), 2.40(m, 4H)  48  ##STR49##  1 Cl Cl oil 46.69(46.82) 3.30(3.29) 8.59(8.54) 7.85-6.83(m, 7H), 5.81-4.90(m, 5H), 4.52(s, 2H), 3.84(d, 2H)  49 ##STR50##  1 Cl Cl oil 37.93(37.77) 3.87(3.81) 6.32(6.38) 7.50-6.90(m, 3H), 5.35(s, 2H),4.80-4.10(m, 6H), 1.35(t, 6H)  50 ##STR51##  1 Cl Cl oil 52.33(52.18)  3.27(3.20) 7.63(7.77) 7.41-6.72(m, 8H), 5.20(s, 2H),4.08(s, 2H)  51 ##STR52##  1 Cl Cl mp 75-76°  C. 48.13(48.25) 3.01(3.11) 7.02(6.90) 7.87-6.80(m, 8H), 5.31(s, 2H),4.58(s, 2H)  52 ##STR53##  1 Cl Cl oil 46.16(46.33) 4.39(4.40) 10.77(10.79) 7.30-6.85(m, 3H), 5.25(s, 2H),4.15(s, 2H), 3.28(q, 4H),1.05(t, 6H)  53 ##STR54##  1 Cl Cl mp 120-122° C. 41.65(41.53) 3.16(3.10) 17.67(17.80) 7.31-6.90(m, 3H), 5.30-4.91(m, 5H), 4.28(s, 2H)  54 ##STR55##  1 Cl Cl mp 35-36°  C. 47.15(47.22) 3.65(3.73) 8.46(8.39) 7.35-6.95(m, 3H), 5.30(s, 2H),4.15(q, 2H), 3.75(s, 2H), 1.20(t, 3H)  55 ##STR56##  1 Cl Cl mp 100-101° C. 56.10(56.37 3.14(3.12) 8.72(8.83) 8.10-7.80(m, 2H), 7.40-6.90(m, 6H), 5.30(s, 2H)  56 ##STR57##  1 Cl Cl mp 79-80°  C. 50.67(50.78) 2.55(2.52) 7.88(7.81) 7.90-7.70(m, 1H), 7.40-6.90(m, 6H), 5.20(s, 2H)  57 ##STR58##  1 Cl Cl mp 98-99°  C. 48.23(48.47) 2.16(2.18) 7.50(7.54) 7.30-6.90(m, 6H), 5.34(s, 2H)  58  ##STR59##  1 Cl Cl oil 49.38(49.48) 2.33(2.30 7.20(7.17) 8.30-8.10(m, 2H), 7.50-6.90(m, 5H), 5.30(s, 2H)  59 ##STR60##  1 Cl Cl mp 79-81°  C. 53.56(53.69) 3.70(3.73) 7.35(7.31) 7.50-6.70(m, 6H), 5.25(s, 2H),3.80(s, 6H)  60 ##STR61##  1 Cl Cl mp 104-105° C. 52.19(52.28) 2.82(2.79) 14.04(14.01) 8.70-8.50(m, 1H), 8.00-6.80(m, 6H), 5.30(s, 2H)  61 ##STR62##  1 Cl Cl mp 94-95°  C. 47.72(47.88) 2.46(2.43) 8.56(8.52) 7.80-6.80(m, 6H), 5.30(s, 2H)  62  ##STR63##  1 Cl Cl mp 91-92° C. 53.27(53.04) 3.87(3.84) 12.42(12.48) 7.25-7.06(m, 3H), 6.60(d, 1H),5.75(d, 1H), 5.40(s, 2H),3.75(s, 3H), 2.20(s, 3H)  63 ##STR64##  1 Cl Cl mp 120-121° C. 58.81(58.66) 3.49(3.45) 8.07(8.10) 7.60-6.80(m, 10H), 5.30(s, 2H)  64 CH.sub. 3 CH.sub.2 O 1 Cl Cl mp 96-97° C. 45.70 3.49 9.69 7.35-6.80(m, 3H), 5.15(s, 2H), (45.98) (3.41) (9.74) 4.33(8, 2H), 1.48(t, 3H) 65 CH.sub.3 CH.sub.2 CH.sub.2 O 1 Cl Cl mp 78-79° C. 47.54 3.96 9.24 7.50-7.20(m, 3H), 5.38(s, 2H),       (47.37) (3.91) (9.32) 4.17(t, 2H), 1.90-1.32(m, 2H),    0.58(t, 3H)  66 ##STR65##  1 Cl Cl mp 94-95°  C. 53.44(53.57) 2.99(3.07) 8.31(8.37) 7.40-7.10(m, 8H), 5.35(s, 2H)  67  ##STR66##  1 Cl Cl mp 97-98°  C. 48.48(48.58) 2.44(2.48) 7.54(7.46) 7.40-6.90(m, 7H), 5.25(s, 2H)  68  ##STR67##  1 Cl Cl mp 75-76°  C. 44.37(44.49) 1.99(1.92) 6.90(6.86) 7.42-6.77(m, 6H), 5.23(s, 2H)  69  ##STR68##  1 Cl Cl mp 70-71°  C. 50.73(50.96) 2.55(2.58) 7.89(7.82) 7.50-6.82(m, 7H), 5.21(s, 2H)  70  ##STR69##  1 Cl Cl mp 81-82°  C. 46.25(46.41) 2.07(2.13) 7.19(7.23) 7.40-6.80(m, 6H), 5.19(s, 2H)  71  ##STR70##  1 Cl Cl mp 59-60°  C. 48.28(28.52) 2.16(2.09) 7.51(7.54) 7.42-6.82(m, 6H), 5.31(s, 2H)  72  ##STR71##  1 Cl Cl mp 84-85°  C. 50.72(50.61) 2.54(2.48) 7.89(7.95) 7.40-6.82(m, 7H), 5.20(s, 2H)  73  ##STR72##  1 Cl Cl mp 58-59°  C. 46.23(46.10) 2.05(2.00) 7.19(7.27) 7.40-6.80(m, 6H), 5.21(s, 2H)  74  ##STR73##  1 Cl Cl mp 43-44°  C. 53.00(53.35) 4.00(4.01) 6.18(6.14) 7.40-6.80(m, 7H), 5.25(s, 2H),4.75(q, 1H), 4.25(q, 2H),1.65(d, 3H), 1.30(t, 3H)  75 H.sub.2 N 1 Cl Cl mp 175-176° C. 41.56 2.71 16.16 7.45-7.05(m, 3H), 5.05(s, 2H),  (71.71) (2.80) (16.27) 2.85(s, 2H)  76 ##STR74##  1 Cl Cl mp 75-76° C. 51.24(54.38) 4.61(4.58) 12.80(12.77) 7.25-6.85(m, 3H), 5.01(s, 2H),3.30(m, 4H), 1.55(m, 6H)  77 ##STR75##  1 Cl Cl mp 118-119° C. 43.73(43.89) 3.01(2.98) 13.90(13.99) 7.45-7.20(m, 3H), 5.25(s, 2H),2.85(bs, 1H), 2.30(s. 3H)  78 ##STR76##  1 Cl Cl mp 90-91° C. 41.53(41.47) 2.85(2.90) 13.21(13.23) 7.65(bs, 1H), 7.60-7.20(m, 3H),5.65(s, 2H), 4.01(s, 3H)  79 ##STR77##  1 Cl Cl mp 136-137° C. 43.39(43.48) 3.34(3.48) 12.65(12.58) 7.30-6.90(m, 4H), 5.30(s, 2H),4.10(q, 2H), 1.25(t, 3H)  80 ##STR78##  1 Cl Cl mp 93-94° C. 43.54(43.31) 3.65(3.69) 16.92(16.90) 9.60(bs, 1H), 7.60-7.20(m, 3H),5.50(s, 2H), 2.90(s, 6H)  81 ##STR79##  1 Cl Cl mp 208-210° C. 41.66(41.42) 3.50(3.41) 17.67(17.81) 7.90(bs, 1H), 7.50-7.10(m, 4H),5.25(s, 2H), 3.22(d, 3H)  82 ##STR80##  1 Cl Cl mp 57-58° C. 41.69(41.93) 2.45(2.44) 14.59(14.56) 8.78(s, 1H), 7.28-6.81(m, 4H),5.19(s, 2H)  83 ##STR81##  1 Cl Cl mp 122-123° C. 46.39(46.57) 3.16(3.21) 10.14(10.19) 8.02-6.83(m, 8H), 5.20(s, 2H),3.42(s, 3H)  84 (CH.sub.3).sub.2 NCHN 1 Cl Cl oil 45.73 3.84 17.78 8.51(s, 1H), 7.37-6.99(m, 3H),       (15.90) (3.85) (17.74) 5.14(s, 2H), 3.21(s, 3H)          3.10(s, 3H)  85  ##STR82##  1 Cl Cl mp 70-71° C. 47.29(47.52) 3.97(3,99) 12.73(12.78) 7.31-6.90(m, 3H), 5.12(s, 2H),4.30(q, 2H), 2.21(s, 2H),1.30(t, 3H)  86  ##STR83##  1 Cl Cl mp 65-66° C. 48.85(48.80) 4.39(4.39) 12.21(12.23) 7.30-6.80(m, 3H), 5.12(s. 2H),4.78(q, 2H), 2.53(q, 2H),1.16(m, 6H)  87  ##STR84##  1 Cl Cl mp 161-162° C. 50.41(50.49) 2.91(2.92) 14.70(14.68) 8.68-8.61(d, 1H), 7.45-6.93(m, 7H), 5.10(s, 2H), 4.92(d, 1H)  88  ##STR85##  1 Cl Cl mp 140-141° C. 46.77(46.52) 2.60(2.69) 7.27(7.11) 7.45-6.74(m, 8H), 5.32(s, 2H)  89 Cl 1 Cl Cl mp 58-59° C. 38.67 1.80 15.03 7.40-7.15(m, 3H), 5.45(s, 2H)       (38.50) (1.86) (15.01) 90 Br 1 Cl Cl mp 62-63° C. 44.28 2.05 11.48 7.38-7.15(m, 3H), 5.40(s, 2H)       (44.16) (2.01) (11.39)  91 ##STR86##  1 Cl Cl mp 99-101° C. 43.52(42.61) 3.65(3.69) 16.92(16.87) 8.70(bs, 1H), 7.35-7.15(m, 3H),5.22(s, 2H), 3.35(s, 3H),2.90(d, 3H)  92  ##STR87##  1 Cl Cl mp 74-75° C. 45.23(45.31) 4.09(4.11) 16.23(16.29) 7.40-7.42(m, 3H), 5.25(s, 2H),3.32(s, 3H), 3.02(s, 6H)  93 ##STR88##  1 Cl Cl mp 110-112° C. 43.59(43.40) 2.66(2.59) 9.24(9.37) 7.51-7.20(m, 3H), 5.62(s, 2H),3.89(s. 3H)  94 ##STR89##  1 Cl Cl mp 94-95°  C. 45.45(45.37) 3.18(3.21) 8.83(8.78) 7.30-6.80(m, 3H), 5.30(s, 2H),4.48(q, 2H), 1.45(t, 3H)  95 ##STR90##  1 Cl Cl mp 162-163° C. 43.73(43.85) 3.00(3.01) 13.91(13.88) 8.80(bs, 1H), 7.50-7.20(m, 3H),5.60(s, 2H), 2.88(d, 3H)  96 ##STR91##  1 Cl Cl mp 90- 91° C. 48.85(48.97) 4.36(4.32) 12.21(12.30) 7.30-6.90(m, 3H), 5.40(s, 2H),3.50(t, 2H), 1.70-1.30(m, 5H),1.05(t, 3H) 97  ##STR92##  1 Cl Cl mp 110-111° C. 47.58(47.42) 3.35(3.34) 12.81(12.92) 7.50-7.00(m, 5H), 5.40-5.20(m, 4H), 4.40-4.00(m, 2H)  98 ##STR93##  1 Cl Cl mp 105-106° C. 39.63(36.89) 2.67(2.68) 18.48(17.37) 7.45-7.10(m, 3H), 6.10(bs, 3H)5.50(s. 2H)  99 ##STR94##  1 Cl Cl mp 104-106° C. 48.85(48.77) 4.40(4.38) 12.20(12.25) 7.50-7.10(m, 3H), 5.45(s, 2H),3.55( q, 4H), 1.25(t, 6H)  100 ##STR95##  1 Cl Cl mp 114-115° C. 45.59(45.64) 3.51(3.48) 13.29(13.32) 7.60-7.30(m, 3H), 5.65(s, 2H),3.05(s, 6H)  101 ##STR96##  1 Cl Cl mp 68-70° C. 43.39(43.16) 3.35(3.32) 12.65(12.61) 7.41-6.70(m, 3H), 5.32(s, 2H),3.70(s, 3H), 3.31(s, 3H)  102 ##STR97##  1 Cl Cl mp 116-118° C. 47.29(47.38) 3.97(4.02) 12.73(12.65) 7.60-7.35(m, 3H), 5.65(s, 2H),3.38(q, 2H), 1.90-7.40(m, 2H),0.98(t, 3H) 103  ##STR98##  1 Cl Cl mp 173-175° C. 41.69(41.64) 2.45(2.47) 14.59(14.62) 7.90(bs, 2H), 7.60-7.30(m, 3H),5.65(s, 2H)  104 ##STR99##  1 Cl Cl mp 103-104° C. 38.24(38.47) 1.61(1.58) 22.29(22.35) 7.45-7.15(m, 3H), 5.25(s, 2H)  105 ##STR100##  1 Cl Cl mp 132-133° C. 45.08(45.21) 2.27(2.29) 14.02(14.05) 9.85(bs, 1H), 8.35-8.15(m, 2H),7.90-7.75(m, 1H), 7.55-7.45(m, 1H),7.45-7. 20(m, 2H), 4.90(s, 2H)  106 ##STR101##  1 Cl Cl mp 157-158° C. 52.77(52.88) 3.05(3.03) 11.53(11.49) 10.45(bs, 1H), 7.90-7.05(m, 8H),5.50(s, 2H)  107 ##STR102##  1 Cl Cl mp 142-143° C. 50.28(50.38) 2.64(2.67) 10.99(10.90) 10.5(bs, 1H), 7.90-6.85(m, 7H),5.62(s, 2H)  108 ##STR103##  1 Cl Cl mp 152-153° C. 48.21(48.45) 2.53(2.57) 10.54(10.60) 10.4(bs, 1H), 7.80-7.05(m, 7H),5.45(s, 2H)  109 ##STR104##  1 Cl Cl mp 128-129° C. 43.66 (43.80) 2.75(2.72) 12.72(12.68) 7.39-7.28(m, 3H), 5.60(s, 2H),4.75(bs, 1H), 2.42(s, 3H)  110 ##STR105##  1 Cl Cl mp 175-176° C. 36.09(36.01) 2.48(2.50) 11.47(11.53) 7.97(bs, 1H), 7.48-7.25(m, 3H),5.60(s, 2H), 3.18(s, 3H)  111 ##STR106##  1 Cl Cl mp 118-119° C. 46.02(46.17) 2.81(2.75) 9.76(9.68) 7.32-6.81(m, 3H), 5.27(s, 2H),2.72(s, 3H)  112 ##STR107##  1 Cl Cl mp 115-116° C. 47.86(47.62) 3.35(3.28) 9.30(9.16) 7.30-6.82(m, 3H), 5.31(s, 2H),3.08(q, 2H), 1.16(t, 3H)  113 ##STR108##  1 Cl Cl mp 54-56°  C. 49.54(49.39) 3.84(3.74) 8.89(8.96) 7.31-6.80(m, 3H), 5.30(s, 2H),3.17(t, 2H), 1.90-1.50(m, 2H),1.06(t, 3H)  114 ##STR109##  1 Cl Cl mp 60-62°  C. 51.08(50.91) 4.29(4.20) 8.51(8.42) 7.32-6.80(m, 3H), 5.31(s, 2H),3.06(t, 2H), 1.70-1.22(m, 4H),0.98(t, 3H)  115 ##STR110##  1 Cl Cl mp 112-113° C. 51.08(50.87) 4.29(4.18) 8.51(8.45) 7.28-6.81(m, 3H), 5.29(s, 2H),3.30-2.90(m, 1H), 1.80-1.20(m, 5H), 0.97(t, 3H)  116 ##STR111##  1 Cl Cl mp 94-96°  C. 56.22(56.01) 3.33(3.27) 7.71(7.80) 7.70-6.81(m, 8H), 5.30(s, 2H),3.88(s, 2H)  117 ##STR112##  1 Cl Cl mp 81-82°  C. 55.04(55.21) 2.89(2.80) 8.02(8.17) 8.10-7.22(m, 8H), 5.72(s, 2H) 118  ##STR113##  1 Cl Cl mp 163-164° C. 43.72(43.88) 2.98(2.91) 13.91(13.95) 12.02(s, 1H), 7.23-7.20(m, 3H),5.69(s, 2H), 2.32(s, 3H)  119 ##STR114##  1 Cl Cl mp 126-127° C. 45.58(45.45) 3.48(3.53) 13.30(13.28) 12.02(s, 1H), 7.23-7.18(m, 3H),5.65(s, 2H), 2.75(q, 2H), 1.23(t, 3H) 120  ##STR115##  1 Cl Cl mp 139-140° C. 47.29(47.37) 3.94(3.97) 12.73(12.68) 12.10(s, 1H), 7.23-7.20(m, 3H),5.42(s, 2H), 2.82(t, 2H),1.68(m, 2H), 1.01(t, 3H)  121 ##STR116##  1 Cl Cl mp 110-112° C. 48.85(48.71) 4.36(4.32) 12.21(12.27) 12.23(s, 1H), 7.29-7.25(m, 3H),5.42(s, 2H), 2.81(t, 2H),1.53(m, 4H), 0.98(t, 3H)  122 ##STR117##  1 Cl Cl mp 155-156° C. 52.76(52.57) 3.02(3.05) 11.54(11.50) 12.23(s, 1H), 7.28-7.24(m, 3H),5.62(s, 2H)  123 ##STR118##  1 Cl Cl mp 80-81° C. 48.85(48.60) 4.39(4.45) 12.21(12.15) 7.30-6.82(m, 3H), 5.30(s, 2H),4.15(q, 2H), 1.40-1.02(m, 6H)  124  ##STR119##  1 Cl Cl oil 50.29(50.12) 4.78(4.70) 11.74(11.62) 7.30-6.82(m, 3H), 5.30(s, 2H),4.16(q, 2H), 2.75(t, 2H),1.72-0.82(m, 8H)  125 ##STR120##  1 Cl Cl mp 98-100° C. 43.73(43.60) 3.00(3.07) 13.91(13.80) 8.92(bs, 1H), 7.42-7.19(m, 3H),5.58(s, 2H), 3.80(s, 3H)  126 ##STR121##  1 Cl Cl mp 84-86° C. 45.59(45.74) 3.51(3.48) 15.18 (15.11) 9.15-8.85(bs, 1H), 7.55-7.25(m, 3H), 5.60(s, 2H), 3.75(q, 2H),1.20(t, 3H)  127 ##STR122##  1 Cl Cl mp 138-139° C. 39.63(39.78) 2.67(2.68) 18.48(18.45) 9.70(bs, 1H), 7.50-7.20(m, 3H),5.50(s, 2H), 2.88(bs, 2H)  128 ##STR123##  1 Cl Cl mp 168-169° C. 41.84(41.76) 2.81(2.79) 19.51(19.55) 7.95(bs, 1H), 7.50-7.25(m, 3H),5.65(s, 2H), 3.30(bs, 2H)  129 ##STR124##  1 Cl Cl mp 139-140° C. 42.25(42.39) 1.78(1.80) 16.42(16.46) 8.70(bs, 1H), 7.40-7.15(m, 3H),5.35(s, 2H)  130 ##STR125##  1 Cl Cl mp 97-99° C. 39.26(39.39) 2.40(2.39) 14.26(14.21) 7.50-7.20(m, 3H), 5.65(s, 2H),4.00(s, 3H)  131 ##STR126##  1 Cl Cl mp 103-104° C. 41.11(41.03) 4.15(4.17) 9.58(9.63) 7.50-7.20(m, 3H), 5.65(s, 2H),3.95(q, 4H), 1.28(t, 6H)  132 ##STR127##  1 Cl Cl mp 32-33°  C. 47.86(47.69) 3.35(3.36) 9.30(9.28) 7.34-6.81(m, 3H), 5.25(s, 2H),3.27--2.64(m, 5H)  133 ##STR128##  1 Cl Cl mp 51-52° C. 41.87(41.72) 3.20(3.27) 20.35(20.19) 7.45-6.75(m, 3H), 5.22(s, 2H),4.45-4.01(m, 1H), 3.35(d, 2H),3.10-2.85(m, 3H)  134 ##STR129##  1 Cl Cl mp 43-44°  C. 46.86(46.94) 4.21(4.17) 8.41(8.46) 7.41-6.75(m, 3H), 5.26(s, 2H),4.40-4.00(m, 2H), 3.50-3.28(m, 5H), 3.15-2.85(m, 3H)  135 Cl.sub.3 C 1 Cl Cl mp 100-102° C. 33.14 1.39 7.73 7.30-6.82(m, 3H), 5.28(s, 2H)       (33.29) (1.31) (7.61)  136 ##STR130##  1 Cl Cl mp 43-44°  C. 50.77(50.43) 4.87(4.74) 8.46(8.54) 7.30-6.82(m, 3H), 5.29(s, 2H),3.02(s, 1H), 1.87(t, 2H), 1.72(s, 3H), 1.60-1.28(m, 2H),0.95(t, 3H) 137  ##STR131##  1 Cl Cl oil 47.55(47.70) 3.99(3.93) 9.24(9,17) 7.30-6.81(m, 3H), 5.28(s, 2H),4.76(q, 1H), 3.30(d, 1H),1.61-1.30(m, 2H), 0.97(t, 3H)  138  ##STR132##  1 Cl Cl oil 49.07(48.87) 4.75(4.67) 8.80(8.63) 7.30-6.80(m, 3H), 5.28(s, 2H),4.85(q, 1H), 2.80(d, 1H),1.90-1.22(m, 4H), 0.96(t, 3H)  139  ##STR133##  1 Cl Cl oil 47.55(47.40) 3.99 (4.07) 9.24(9.35) 7.30-6.82(m, 3H), 5.29(s, 2H),3.02(bs, 1H), 1.60(s, 6H)  140 ##STR134##  1 F Cl oil 60.29(60.12) 3.77(3.70) 8.79(8.92) 7.22-6.80(m, 8H), 5.20(s, 2H),4.09(s, 2H)  141 ##STR135##  1 F Cl oil 57.07(7.23) 3.27(3.21) 8.32(8.15) 7.40-6.70(m, 7H), 5.20(s, 2H),4.02(s, 2H)  142 CH.sub.3 CH.sub.2 CH.sub.2 1 F Cl oil 53.24 4.44 10.35 7.20-6.85(m, 7H), 5.26(s, 2H),       (53.02) (4.35) (10.27) 2.66(t, 2H), 2.06-1.38(m. 2H),          0.93(t, 3H)  143 ##STR136##  1 Cl F oil 60.29(60.02) 3.77(3.68) 8.79(8.87) 7.30-6.85(m, 8H), 5.35(s, 2H),4.05(s, 2H)  144 CH.sub.3 CH.sub.2 CH.sub.2 1 Cl F oil 53.24 4.44 10.35 7.20-6.80(m, 7H), 5.20(s, 2H),       (53.10) (4.38) (10.21) 2.65(t, 2H), 2.06-1.35(m, 2H),          0.95(t, 3H) 145 CH.sub.2CHCH.sub. 2 1 Cl F oil 53.64 3.73 10.43 7.23-6.75(m, 3H), 6.34-5.79       (53.49) (3.70) (10.48) (m, 3H), 5.28(s, 2H), 3.58(d, 2H)  146 ##STR137##  1 Cl F oil 54.41(54.48) 2.83(2.81) 7.93(7.86) 7.32-6.72(m, 7H), 5.21(s, 2H),4.02(s, 2H)  147 ##STR138##  1 Cl F oil 57.07(57.30) 2.97(2.95) 8.32(8.37) 7.32-6.62(m, 7H), 5.23(s, 2H),4.02(s, 2H)  148 CH.sub.3 CH.sub.2 CH.sub.2 1 CH.sub.3 Cl mp 44-45° C. 58.54 5.67 10.50 7.15-6.67(m, 3H), 5.15(s, 2H), (58.39) (5.65) (10.58) 2.78(t, 2H), 2.24(s, 3H),          2.09-1.56(m, 2H), 1.02(t, 3H) 149 ClCH.sub.2 1 CH.sub.3 Cl mp 30-31° C. 48.37 3.66 10.26 7.32-6.72(m, 3H), 5.29(s, 2H),       (48.18) (3.69) (10.22) 4.76(s, 2H), 2.25(s, 3H)  150 ##STR139##  1 CH.sub.3 Cl oil 52.62(52.75) 4.39(4.43) 9.45(9.40) 7.32-6.72(m, 3H), 5.33(s, 2H),5.32(s, 2H), 2.33(s, 3H),2.31(s, 3H)  151 HOCH.sub.2 1 CH.sub.3 Cl mp 71-72° C. 51.88 4.32 11.00 7.32-6.72(m, 3H), 5.32(s, 2H),       (51.64) (4.35) (11.04) 4.82(s, 2H), 4.28(bs, 1H), 2.32(s, 3H)  152 ##STR140##  1 CH.sub.3 Cl mp 64-65° C. 53.33(53.18) 3.40(3.42) 7.31(7.28) 7.32-6.65(m, 6H), 5.23(s, 2H),5.22(s, 2H), 2.32(s, 3H)  153 CH.sub.3 CH.sub.2 O 1 CH.sub.3 Cl mp 86-87°  C. 53.64 4.88 10.42 7.20-6.80(m, 3H), 5.10(s, 2H),       (53.57) (4.81) (10.47) 4.33(q, 2H), 2.21(s, 3H),          1.46(t, 3H)  154 ##STR141##  1 CH.sub.3 Cl mp 90-91° C. 52.62(52.47) 4.43(4.42) 9.44(9.49) 7.08-6.45(m, 3H), 4.45(q, 2H),2.10(s, 3H), 1.41(t, 3H)  155 ##STR142##  1 CH.sub.3 Cl mp 129-130°  C. 51.16(51.43) 4.30(4.33) 14.91(14.95) 7.70-7.40(bs, 1H), 7.40-6.70(m, 3H), 5.65(s, 2H), 2.78(d, 3H),2.10(s, 3H)  156 ##STR143##  1 CH.sub.3 Cl mp 87-88° C. 52.79(52.70) 4.78(4.82) 14.20(14.15) 7.40-6.70(m, 3H), 5.65(s, 2H),2.90(s, 6H), 2.10(s, 3H)  157 ##STR144##  1 CH.sub.3 Cl mp 108-109°  C. 55.64(55.49) 5.61(5.59) 12.97(13.00) 7.40-6.70(m, 3H), 5.65(s, 2H),4.03(q, 4H), 2.10(s, 3H),1.20(t, 6H)  158 CH.sub.3 CH.sub.2 CH.sub.2 3 CH.sub.3 Cl mp 31-32° C. 64.12 6.50 9.50 7.10-6.60(m, 3H), 3.96(t, 2H),       (64.28) (6.48) (9.44) 2.99(t, 2H), 2.80-1.62(m, 7H),    0.94(t, 3H) 159 ClCH.sub.2 3 CH.sub.3 Cl oil 51.84 4.65 9.31 7.31-6.62(m, 3H), 4.63(s, 2H),       (51.67) (4.60) (9.36) 4.02(t, 2H), 3.17(t, 2H),          2.42-2.12(m, 5H)  160 ##STR145##  3 CH.sub.3 Cl oil 55.48(55.33) 5.24(5.21) 8.63(8.65) 7.31-6.58(m, 3H), 5.28(s, 2H),3.98(t, 2H), 3.17(t, 2H),2.43-2.02(m, 8H)  161 HOCH.sub.2 3 CH.sub.3 Cl mp 65-66° C. 55.28 4.96 9.91 7.27-6.51(m, 3H), 4.73(s, 2H),       (53.37) (4.95) (9.95) 4.55(bs, 1H), 4.01(t, 2H), 3.12     (t, 2H), 2.67-2.10(m, 5H) 162 CH.sub.3 CH.sub.2 O 3 CH.sub.3 Cl mp 60-61° C. 56.66 5.76 9.44 7.30-6.78(m, 3H), 4.62-4.10 (56.41) (5.81) (9.47) (m, 4H), 3.25(t, 2H), 2.83-2.41          (m, 5H), 1.71(t, 3H)  163 ##STR146##  3 CH.sub.3 Cl mp 52-54° C. 55.47(55.58) 5.29(5.32) 8.62(8.58) 7.00-6.40(m, 3H), 4.43(q, 2H),3.98(t, 2H), 3.23(t, 2H), 2.60-2.20(m, 2H), 2.20(s, 3H), 1.45(t, 3H)  164 ##STR147##  3 CH.sub.3 Cl mp 98-99° C. 54.28(54.41) 5.22(5.18) 13.56(13.62) 7.55(bs, 1H), 7.00-6.40(m, 3H),3.98(t, 2H), 3.23(t, 2H), 2.78(d, 3H), 2.40(m, 2H), 2.10(s, 3H)  165 ##STR148##  3 CH.sub.3 Cl oil 55.64(55.49) 5.61(5.59) 12.97(13.01) 7.00-6.40(m, 3H), 7.98(t, 2H),3.23(t, 2H), 2.90(s, 6H), 2.60-2.20(m, 2H), 2.10(s, 3H)  166 ##STR149##  3 CH.sub.3 Cl oil 58.03(57.88) 6.32(6.29) 11.94(11.97) 7.00-6.40(m, 3H), 4.15-3.80(m, 6H), 3.23(t, 2H), 2.60-2.20(m, 2H), 2.20(s, 3H), 1.20(t, 6H)  167 CH.sub.3 CH.sub.2 CH.sub.2 3 Cl Cl oil 53.35 5.12 8.89 7.11-6.62(m, 3H), 3.95(t, 2H),       (53.48) (5.09) (8.83) 2.97(t, 2H), 2.70-2.10(m, 4H),          1.90-1.50(m, 2H), 0.98(t, 3H) 168 ClCH.sub.2 3 Cl Cl oil 44.85 3.42 8.71 7.31-6.65(m, 3H), 4.73(s, 2H),       (44.72) (3.49) (8.73) 4.01(t, 2H), 3.12(t, 2H),          2.67-2.10(m, 2H)  169  ##STR150##  3 Cl Cl oil 48.71(48.87) 4.06(4.03) 8.12(8.16) 7.31-6.65(m, 3H), 5.12(s, 2H),4.08(t, 2H), 3.15(t, 2H),2.51-2.12(m, 5H)  170 HOCH.sub.2 3 Cl Cl mp 74-75° 47.54 3.96 9.24 7.31-6.65(m, 3H), 4.73(s, 2H),    (47.32) (3.94) (9.28) 4.55(bs, 2H), 4.01(t, 2H), 3.12          (t, 2H), 2.67-2.10(m, 2H)  171 ##STR151##  3 Cl Cl oil 50.07(50.21) 3.25(3.22) 6.49(6.45) 7.31-6.62(m, 6H), 5.23(s, 2H),4.02(t, 2H), 3.17(t, 2H), 2.42- 2.12(m, 2H)  172 ##STR152##  3 Cl Cl mp 57-58°  C. 48.71(48.55) 4.09(4.05) 8.11(8.16) 7.00-6.40(m, 3H), 4.43 (q, 2H),3.98(t, 2H), 3.23(t, 2H), 2.60-2.20(m, 2H), 1.45(t, 3H)  173  ##STR153##  3 Cl Cl mp 90-92° C. 47.29(47.48) 3.98(3.92) 12.72(12.61) 7.55(bs, 1H), 7.00-6.40(m, 3H),3.98(t, 2H), 3.23(t, 2H), 2.78(d,3H), 2.60-2.20(m, 2H), 2.10(s, 3H)  174 ##STR154##  3 Cl Cl mp 60-61° C. 48.85(48.99) 4.40(4.38) 12.20(12.09) 7.00-6.40(m, 3H), 3.98(t, 2H),3.23(t, 2H), 2.90(s, 6H),2.60-2.20(m, 2H) 
    
     The compounds of the present invention may be used as they are but normally they are used in the form such as wettable powders, dusts, emulsion concentrates, suspension concentrates, or granules. These formulations may be used as they are or may be used after dilution with water. 
     When liquid formulations are applied, the solvent such as water, alcohol, ether, acetone, ester, amide or petroleum ether may be used. As the solid carrier, an inorganic powder such as magnesium lime, gypsum, calcium carbonate, silica, alumina, zeolite, clay mineral and resin powder may be used. 
     The dosage of the present invention to be used as an active ingredient may be varied depending on the type of formulation, the manner for application, the timing and the weather condition. The dosage is usually varied in the range of 0.25 to 4 Kg/ha. 
     The compounds of the present invention are sufficiently effective even if they are applied solely. However, their application in combination with one or more types of compounds having herbicidal activity makes it possible not only to reduce the amount of the active ingredient, but also to attain the enlargement of the herbicidal spectrum or improve the effects. 
     The typical examples of herbicides that can be used together with the compounds of the present invention are mentioned, for examples, amide-type herbicides such as monalide, propanil, solan, diphenamide, fluoridamide, mefluidine, benzamizole, butachlor and alachlor; dinitroaniline-type herbicides such as trifluralin, benfluralin, profluralin, isopropaline, pendimenthalin and ethalfluralin; urea-type herbicides such as buturon, monolinuron, parafluron, tetrafluron, linuron, sulfodiazol, buthiuron, chlorosulfuron and sulfomethuronmethyl; carbamate-type herbicides such as chlorobufam, barban, diallate, phenmedipham, butylate, triallate, bentiocarb and methylbencarb; diphenylether-type herbicides such as oxyfluorofen, acifluorfornethyl, lactofen, formesafen and fluoronitrofen; and diazine-type herbicides such as oxadiazon and immazaqium. 
     FORMULATION EXAMPLES 
     Some examples of the formulations are given below. 
     Formulation 1 
     Emulsion Concentrate 
     30 parts of compound No. 1 of the present invention, 60 parts of m-xylene and 10 parts of surfactant mixture(polyoxyethylene alkyl aryl ether and sodium alkyl aryl sulfate) were uniformly mixed and stirred to obtain an emulsion concentrate. 
     Formulation 2 
     Wettable Powder 
     10 parts of compound No. 4 of the present invention, 85 parts of white carbon and 5 parts of surfactant mixture(polyoxyethylene alkyl aryl ether sulfate and polyoxyethylene alkyl and aryl ether) were mixed and pulverized to obtain a wettable powder. 
     Formulation 3 
     Granule 
     3 parts of compound No. 100 of the present invention, 60.0 parts of bentonite, 35 parts of talc, 0.5 parts of sodium dodecyl benzene sulfonate, 0.5 parts of sodium metasilicate and 1.5 parts of sodium tripolyphosphate were mixed, and after an addition of a proper amount of water, kneaded. The mixture was granulated by using an extrusion granulating machine and dried by a conventional method to obtain granules. 
     TEST EXAMPLE 
     Test Example 1 
     Herbicidal Test Against Paddy Field Weeds 
     Paddy field soil was filled in 140 cm 2  plastic pot and irrigated. Paddy rice seedlings (Variety: Dongjin) of 2.5 leaf stage were transplanted and some amounts of paddy field weeds were also sown. On the second day after the transplantation, the predetermined amounts of the compounds of the present invention were applied in the form of wettable powder. 
     During the test period, 2 cm in height of water from the surface of the soil in pot was maintained. Upon twentieth day after the treatment with compound of the present invention, the herbicidal effects against the weeds and phytotoxicity against paddy rice plants were examined. The results are shown in table 2 and herbicide rating system is shown in table 3. 
     
                                           TABLE 2__________________________________________________________________________4 kg/haCompoundNO.   ORYSA      ECHOR           SCPJU               BR.s                  ANEKE                       MOOVA                            CYPDI                                 CYPSE                                      SAGPY__________________________________________________________________________ 1    70    95         100  100  100 2    40   100         100  100  100 3    10    50   0      70        10 4    30   100  100    100  100  100 5    30    90  100    100  100  100 6    40   100  100 100               100   20 7    20   100   90    100  100  100 8     0   100   50    100  100   70 9    20   100  100    100  100  10010    30   100  100    100  100  10011    30   100  100    100  100  10012    20   100  100    100  100  10013     0   100  100    100  100  10014     0    80   70    100  100   8015    30   100   90    100   90  10016      0   90  100    100   90  10017    30   100  100    100  100  10018    50   100  100    100  100  10019    80   100  100 100                    10020    20   100  100    100  100  10021    10   100  100 100               100  10022    60   100  100 100               100  10023    10   100  100 100               100  10024    10   100  100 100               100  10025    10   100  100 100               100  10026    10   100  100 100               100  10027    10   100  100 100               100  10028     0   100  100 100               100   2029    20   100  100 100                70  10030    80   100  100 100               100  10031    40   100  100 100               100  10032    30   100   90              100  100   7033    30   100  100 100                    10034    50   100  100 100                    10035    60   100  100 100               100  10036    60   100  100 100               100  10037    60   100  100 100               100   5038    10   100  100 100               100  10039    10   100  100 100               100  10040    70   100  100    100  100  10041    70   100  100    100  100  10042    50    80  100    100  100  10043    50   100  100 100                    10044    50   100  100 100                    10045    10   100  100 100               100   7046     0    40   70  5047    20   100  100 100               100  10048    10   100  100 100               100  10049    10   100  100    100  100   5050    40   100   90 100                     5051    20   100   80 100                     2052    40   100  100 100               100   9053    70   100  100    100  100  10054    40    80  100    100  100  10055     0    50   20    100   90   6056    20    90   90    100  100   8057     0   100   90    100  100  10058    40    70   20     80   70   5059    30    70   70     80   80   8060    20    80  100    100  100  10061    40    80   90    100  100  10062    10    90   90    100  100  10063    20    90  100    100  100  10064    60   100  100    100  100  10065    50   100  100    100  100  10066    40   100  100    100  100  10067    10   100  100    100  100  10068    20   100   90 100                     069    40   100  100 100               100  10070    30   100   90 100               100   8071    50   100  100 100               100  10072    10   100  100 100               100  10073    10   100  100 100               100  10074    60   100  100 100               100  10075    100  100         100  100  10076    10    90   90    100   90  10077    60   100         100  100  10078    80   100  100    100  100  10079    40   100         100  100  10080    40   100  100 100               100   8081    40   100  100 100               100   6082    50   100  100 100               100  10083    10    60   50  60                50   5084    10    80   90 100                60   9085    50   100   90 100               100  10086    60   100  100 100               100  10087    40   100  100 100                90  10088     0    50   0   30                0    089    70   100  100 100               100  10090    60   100  100 100               100  10091    10   100  100 100               100  10092    10   100  100 100               100  10093    60   100  100 100               100  10094    30   100  100    100  100  10095    50   100  100 100               100   9096    40   100         100  100   7097    60   100         100  100  10098    60   100         100  100  10099    20   100  100    100  100   90100   60   100  100    100  100  100101   80   100  100 100               100  100102   50   100  100    100  100  100103   60   100  100 100               100  100104   60    90         100  100   90105   50   100  100    100  100  100106    0   100   80  80                     0107   20   100  100  80                     30108   10   100   70 100                     0109   60   100  100 100               100  100110   60   100  100 100                    100111   10   100  100 100               100  100112   50   100  100 100               100  100113   60   100  100 100               100  100114   10   100  100 100               100  100115   10   100  100 100               100  100116   10   100  100 100               100  100117   10   100  100 100               100  100118   10   100  100 100               100  100119   60   100  100 100                    100120   60   100  100 100               100  100121   10   100  100 100               100  100122   10   100  100 100               100  100123   30   100  100 100               100   60124   50   100  100 100               100   70125   70   100   60 100                90  100126   70   100  100 100               100  100127   60   100  100 100               100  100128   60   100  100 100                    100129   70   100  100 100                    100130   80   100  100 100               100  100131   60   100  100 100                    100132   50   100  100 100                80   90133   40   100   90 100               100   80134   50   100  100 100               100   80135   30   100  100 100               100  100136   10   100  100 100               100  100137   10   100  100 100               100  100138   10   100  100 100               100  100139   10   100  100 100               100  100140   40    90   80 100                90   0141   50   100   90 100               100   0142   50   100   80 100               100   0143   70   100  100 100               100   80144   70   100  100 100               100   90145   70   100  100 100               100  100146   60   100  100 100               100   70147   60   100  100 100               100   90148   10   100  100 100               100  100149   10   100  100 100               100  100150   80   100  100 100               100  100151   10   100  100 100               100  100152   10   100  100 100               100  100153   50   100  100 100               100  100154   90   100  100 100               100  100155   10   100  100 100               100  100156   10   100  100 100               100  100157   10   100  100 100               100  100158   20   100  100    100  100  100159    0    20   80  90                90   20160   30    70  100 100                70161   40   100  100 100                70  100162   40    60  100 100               100   70163   60    80  100 100               100  100164   10    40  100 100                50   90165    0     60 100 100                90  100166    0    40   90 100                80   90167   30   100  100    100  100  100168   10    60   50  60                50   50169   20   100  100 100                50   90170    0   100   90 100                0    60171   10    80   40 100                0    0172   20    90  100  60               `50   50173    0    50   90 100                0    0174    0    80   90 100                0    70__________________________________________________________________________ *BR.s: mixture of annual broad leaf weeds such as ANEKE (dayflower), MOOV (monochoria), ROTIN (toothcup) etc. 
    
     
         ______________________________________PADDY WEED SPECIES                       ENGLISHABRV.  GENUS-SPECIES NAME   NAME______________________________________ORYSA  Oryza sativa L.      RiceECHOR  Echinochloa crus-galli                       Barnyardgrass  P. BEAUV. var. oryzicola OHWISCPJU  Scirpus juncoides ROXB.                       BulrushCYPDI  Cyperus difformis L. UmbrellaplantCYPSE  Cyperus serotinus ROTTB.                       Flat-sedgeANEKE  Aneilema keisak HASSK.                       DayflowerMOOVA  Monochoria vaginalis PRESL.                       MonochoriaROTIN  Rotala indica KOEHE. ToothcupSAGPY  Sagittaria pygmaea MIQ.                       Arrow head______________________________________ 
    
     
                                           TABLE 3__________________________________________________________________________Herbicide Rating SystemRatingDescriptionPercentof Main      Crop         WeedControlcategories      Description  Description__________________________________________________________________________ 0   No effect      No crop reduction                   No weed control      or injury10   Slight      Slight discoloration                   Very poor weed controleffect      or stunting20         Some discoloration,                   Poor weed control      stunting or stand loss30         Crop injury more                   Poor to deficient weed      pronounced but not                   control      lasting40   Moderate      Moderate injury, crop                   Deficient weed controleffect      usually recovers50         Crop injury more                   Deficient to moderateeffect      lasting, recovery                   weed control60         Lasting crop injury                   Moderate weed control      no recovery70   Severe      Heavy injury and stand                   Control somewhat lesseffect      loss         than satisfactory80         Crop nearly destroyed                   Satisfactory to good      a few survivors                   weed control90         Only occasional live                   Very good to excellent      plants left  control100  Complete      Complete crop                   Complete weedeffect      destruction  destruction__________________________________________________________________________