SUBSTITUTED N-AROYL N'-PHENYL UREA COMPOUNDS

Abstract: Novel N-aroyl N′-phenyl ureas having halogen or alkyl substituents in the 3- and 5-positions and haloalkyl, haloal­ koxy or haloalkylthio in the 4-position of the N′-phenyl are more active and have a broader spectrum of effectiveness than the known benzoylurea insecticides.

Description: SUBSTITUTED N-AROYL N'-PHENYL UREA COMPOUNDS This invention relates to novel substituted N-aroyl N'-phenyl ureas, a process for producing them, insecticidal compositions containing them and a method for controlling certain insects. Various insecticidal derivatives of urea are known in the art, such as, for example, U.S. Patents 4,173,638; 4,005,223; 4,170,657; 4,139,636; 4,089,975 and German Patent Application 3,003,113. The N-aroyl N'-phenyl ureas of the present invention are more active and have a broader spectrum of effectiveness than the benzoylurea insecticides currently available. The novel compounds of this invention are N-aroyl N'-phenyl ureas having the formula EMI1.1 wherein: Ar is a substituted phenyl, pyridyl or pyrimidinyl radical wherein the substituents are chloro, bromo, fluoro, C1-C3 alkyl or C1-C3 alkoxy, with the proviso that at least one substituent is positioned ortho to the carbonyl group; R3 and R4 are individually B or C1-C4 alkyl or together they. form the group EMI2.1 Y is O or S; X1, X2, X3 and X4 are individually H, halogen, C1-C3 alkyl, C1-C3 alkoxy, alkylcarbonyl, alkoxycarbonyl, C1-C3 alkylthio, NO2, CN or NR5R6 wherein R5 and R6 are H or C1-C3 alkyl with the provisos that at least one of X1, X2, X3 or X4 is other than H and (a) when three of X1, X2, X3 or X4 are , the fourth substitution cannot be halogen or alkyl, (b) when X1 and X3 are H, X2 and X4 cannot both be halogen, (c) when X2 and X3 are H, X1 and X4 cannot both be halogen and R is a C1-C4 haloalkyl, haloalkoxy or haloalkylthio group. These novel compounds can be prepared by methods analogous to those known in the art, e.g., as taught in U.S. Patent 4,139,636. The invention also provides insecticidal compositions comprising an insecticidally effective amount of the above described N-aroyl N'-phenyl ureas in admixture with a suitable carrier or adjuvant therefore and a method for killing and/or controlling insects which comprises applying the active compound, alone or in admixture with a carrier, to the insects, the insect larvae or their habitats. The preferred compounds of this invention are those having the formula EMI3.1 where R1 is F or C1; R2 is F, C1 or H; Y is O or S; X1 is H, C1 or CE3; X2 and X3 are H, C1, CH3 or OCH3 and R is CF3, OCF3, OCF2CHF2, OCF2CHC1F or OCF2CRFBr. Most preferably, Y is O, R1 and R2 are both fluorine, X2 and X3 are C1 or CH3 and R is OCF2CHC1F, OCF2CHF2 or OCF2CHFBr. Particularly preferred compounds are those wherein X1 and X2 are C1 and X3 is H; X1 and X3 are CH3 and X2 is H; and X2 and X3 are CH3 or C1 and X1 is H. The compounds of the present invention are normally crystalline solids of low solubility in water and of moderate solubility in many organic solvents. The compounds have low phytotoxicity and have exceptional activity in the control of various undesirable agricultural, household and veterinary insect pests. Representative of the various insects which can be controlled by the active compounds of the present invention are members of the orders Lepidoptera, Coleoptera, Diptera, Orthoptera, Homoptera, Thysanoptera and Acarina. They are active against normally sensitive and resistant species at some stages of development. Examples of insect pests comprising the above include the tobacco budworm (Beliothis virescens), the beet armyworm (Spodoptera exigua), the Egyptian cotton leafworm (Spodoptera littoralis), the American bollworm (Heliothis armigera), the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the cutworm (Agrotis segetum), the Mediterranean flour moth (Ephestia kuehniella), the Colorado potato beetle (Leptinotarsa decimlineata), the mustard beetle (Phaedon cochleariae), the cotton boll weevil (Anthonomus grandis), the Mexican bean beetle (Epilachna varivestis), the khapra beetle (Trogoderma granarium), the housefly (Musca domestica), the lesser housefly (Fannia canicularis), the Mediterranean fruit fly (Ceratitis capitata), the black blow fly (Phormia regina), the cabbage rootfly (Hylemya brassicae), the yellow fever mosquito (Aedes aegypti), the malaria mosquito (Anopheles stephensi), the desert locust (Schistocerca gregaria), the migratory locust (Locusta migratoria), the German cockroach (Blattells germanica), the American cockroach (Periplaneta americana), the pear psylla (Psylla pyricola), the onion thrips (ThriPs tabaci), and the citrus rust mite (PhYllocoptruta oleivora). The compounds are highly active and can be employed to kill insects outright and/or to prevent adult emergence from juvenile forms of the insect. In such applications, the insect to be controlled and/or its habitat is contacted or treated with an insecticidal amount of one or more of the compounds of the present invention. The compounds may be administered orally to warm blooded animals from which they are excreted unchanged and they effectively combat the larvae of certain feces inhabiting insects, e.g., the face fly, horn fly and buffalo fly. For all such uses, these compounds can be employed in unmodified form. However, the present invention embraces the use of an insecticidally-effective amount of the active ingredients in composition form with a material known in the art as an adjuvant or carrier. Thus, for example, compositions employing one or a combination of these active ingredients can be in the form of a liquid or a dust; and the adjuvant employed can be any one of a plurality of materials including aromatic solvents, petroleum distillates, water or other liquid carriers, propellant substances, surface-active dispersing agents, light absorbers and finely-divided carrier solids. The exact concentration of one or a combination of the compounds of the present invention in a composition thereof with an adjuvant therefore can vary; it is only necessary that one or a combination of the compounds be present in a sufficient amount so as to make possible the application of an insecticidally-effective or inactivating dosage. Generally, for practical applications, one or a combination of these active ingredients can be broadly applied to the insect larvae or their habitat in compositions containing from about 0.0001 to about 98 percent by weight, preferably 5 to 50 percent by weight, of the compounds. The invention is further illustrated by the following examples. Example 1 - 3,5-Dichloro-4-(2,2-dichloro-1,1-difluoro- ethoxy)phenyl isocyanate 3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)benzenamine (12 g, 0.04 mole) was added to a solution of 20 g oxalyl chloride in 100 ml CC14 and heated under reflux with stirring for 0.5 hour. A solid precipitated. The carbon tetrachloride and excess oxalyl chloride were removed by evaporation in a rotary evaporator. The residue (16 g) was a slightly oily white solid, which was used in the next reaction without purification. Example 2 - 2-Chloro-N-( ((3, 5-dichloro-4-(2, 2-dichloro- 1,1-difluoroethoxy)phenyl)amino)carbonyl -3-pyridinecarboxamide EMI6.1 2-Chloro-3-pyridinecarboxamide (6.3 g, 0.04 mole) and 3,5-dichloro-4-(2,2-dichloro-1,1-dichloro- ethoxy)phenyl isocyanate (crude; 16 g, 0.04 mole) were added to 250 ml xylene and heated under reflux with stirring for two hours. After cooling in ice water, the precipitated product was removed by suction filtration. This was recovered as 2-chloro-3-pyridine carboxamide. A second crop was obtained by adding about 400 ml hexane to the filtrate. The second crop was a mixture of the desired material and recovered amide. The desired material was isolated and purified by recrystallizing twice from toluene. M.P. = 189-1920C. NMR spectral features supported the structural assignment. Example 3 - N-( ((3, 5-Dichloro-4-(2,2-dichloro-l, 1- -difluoroethoxy)phenyl )amino )carbonyl )- -2, 6-difluoro-N-methylbenzamide EMI7.1 N-(((3,5-Dichlor-4-(2,2-dichlor-1,1-difluoroethoxy)phenyl)amino)carbonyl)-2,6-difluorobenzamide (9.9 g, 0.02 mole) and KOH (1.4 g, 87 percent purity, 0.02 mole) were added to 50 ml dimethylformamide with stirring, giving a clear solution. Iodomethane (3.2 g, 0.022 mole) was added and the resulting solution was stirred at room temperature for about 24 hours. The precipitated product was collected by suction filtration and dried. The product was purified by recrystallization from isopropanol. The purified product was a white solid melting at 153-155 C. NMR spectral features support the structural assignment. Elemental Analysis: Calcd: C, 40.18; H, 1.98; N, 5.51 Found: C, 40.3; H, 2.10; N, 5.43 Example 4 - (A) Preparation of 2,6-diethyl-4-nitrophenol A solution of 45 g (0.3 mole) of 2,6-diethylphenol in 300 ml of chloroform was prepared in a 500 ml, 3-necked round bottom flask fitted with a mechanical stirrer, thermometer and dropping funnel and 27 g (0.3 mole) of 70 percent ENO3 was added dropwise with stirring and cooling at 250-300C in 1/2 hour. Stirring at room temperature was continued for 5 hours. The mixture was washed with 100 ml of water and the solvent removed in a rotary evaporator. A dark red oil (86 g) was obtained which partially crystallized on standing. This was cooled in an ice water bath and the resulting solid removed by suction filtration. The cake (A) was washed with cold chloroform and dried at room temperature (19 g). NMR indicated the product was 2,6-diethyl-4 -nitrophenol (93 percent pure). The solvent was removed from the filtrate in a rotary evaporator leaving 43 g of residue (B). Gas chromatography indicated 47 percent starting material, 22 percent desired product, plus two higher products. (B) was dissolved in 200 ml chloroform, returned to the reactor and 13 ml of HNO3 was added dropwise with stirring in 5 minutes. The temperature rose from 230 to 300C. Stirring at room temperature was continued for 5 hours and the mixture worked up as above. 62 Grams of a dark red oil (C) was obtained which was placed in the refrigerator overnight. Suction filtration provided 5 grams of solid (D). (B) Preparation of 4-amino-2,6-diethyl phenol HCl Cake (A) and solid (D) were combined (24 g) and placed in a Pyrex bottle with 200 ml of 95 percent ethanol and 2 g of 5 percent palladium on carbon catalyst and hydrogenated in a Parr apparatus at 30-50 psig for 2.75 hours using a heat lamp. Hydrogenation almost stopped when 16 psig hydrogen absorbed. Two more grams of catalyst were added and hydrogenation was continued for 1.33 hours when hydrogenation stopped. An additional 20 psig hydrogen absorbed, although there was a small leak in the apparatus. The mixture was cooled and suction filtered to remove the catalyst which was washed with some ethanol. The ethanol was removed from the filtrate in a rotary evaporator. The residue, a brown, oily, low-melting solid, weighed 28 g. The solid was dissolved in 250 ml of methylene dichloride which was then saturated with dry HC1 while cooling in an ice water bath. After filtering with suction, the resulting cake was washed with cold methylene dichloride and dried at room temperature. 16 Grams of a tan solid was obtained, m.p. 2300-2350C. The yield was 66 percent and the structure was confirmed by NMR. (C) Preparation of 4-(2-chloro-1,1,2-tri fluoroethoxy)-3,5-diethylbenzenamine The above tan solid (16 g) was placed in a 500 ml round bottom flask fitted with a mechanical stirrer, thermometer, reflux condenser and sparger, along with 150 ml of dimethylformamide and 9.0 g (0.16 mole) of KOH pellets which were ground to powder. The mixture was heated while stirring to 900C and 12 g (0.1 mole) of chlorotrifluoroethylene was bubbled in at 900-1000C in 35 minutes. Stirring was continued at about 900C for 5 minutes, the mixture was cooled with an ice water bath and 300 ml of cold water was added. The mixture was extracted with 200 ml of methylene dichloride and then 100 ml of methylene dichloride. The extracts were combined, washed with 250 ml of water and the methylene dichloride removed in a rotary evaporator. The residue was distilled through a short column. The second cut (1200-1300C/2 mm) was a light tan viscous liquid weighing 9 g. The structure was confirmed by NMR and the yield was 40 percent. (D) Preparation of N-(((4-(2-chloro-1,1,2- -trifluoroethoxy)-3,5-diethylphenyl) amino )carbonyl )-2 , 6-difluorobenzamide The light tan liquid prepared above (9 g, 0.03 mole) was dissolved in 150 ml toluene in a 500 ml, 3-necked round bottom flask fitted with a mechanical stirrer, thermometer and reflux condenser and 7.3 g (0.04 mole) of 2,6-difluorobenzoyl isocyanate was added while stirring. The temperature rose from 210 to 260C. The mixture was heated at reflux for 1 hour and filtered hot through fluted filter paper to remove a trace of dirt. The filtrate was cooled in an ice water bath and the upper solvent layer decanted off about 1 g of a brown gum. The toluene was removed in a rotary evaporator leaving a residue of 17 g of a dark brown viscous oil to which 25 ml of isopropanol was added. Upon heating to boiling, a clear solution developed which was cooled in an ice water bath. The resulting crystals were removed by suction filtration, the filter cake was washed with cold isopropanol and dried at room temperature. A light tan solid (6.5 g, m.p. 1220-1240C) was obtained. The structure was confirmed by NMR. Analysis: Calcd: C, 51.68; H, 3.90; N, 6.03. Found: C, 51.5; H, 3.93; N, 6.04 Employing the above procedures and appropriate starting materials, the following compounds were prepared: N-(((3,5-Dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl)amino)carbonyl)-3,5-dichlor-4-pyrimidinecarboxamide. EMI11.1 M.P.= 217 -219 C. N-(((3,5-Dichloro-4-(1,1,2,2-tetrafluoroethoxy)- phenyl)amino)carbonyl)-2,6-difluorobenzamide. EMI11.2 M.P. = l970-l990C. Analysis: Calcd: C, 41.67; H, 1.75; N, 6.08 Found: C, 41.8; H, 1.92; N, 6.06 N-(((3,5-Dichloro-4-(1,1,2,2,-tetrafluorethoxy)phenyl)amine)carbonyl)-2-chlorobenzamide. EMI12.1 M.P. = 1730-l750C Analysis: Calcd: N, 6.10 Found: N, 6.34 N-(((3,5-Dichloro-4-/2,2-dichlor-1,1-difluorethoxy)phenyl)amino)carbonyl)-3,5-dichloro-4-pyridinecarboxamide. EMI12.2 M.P. = 2280-2300C. N-(((3,5-Dichloro-4-(2,2-dichloro-1,1-difluoro- ethoxy)phenyl)amino)carbonyl)-2-methoxybenzamide. EMI12.3 M.P. = 1560-1580C. Analysis: Calcd: 41.83% C; 2.48% H; 5.74% N. Found: 41.9% C; 2.57% H; 5.92% N N-(((3,5-Dichlor-4-(2,2-dichlor-1,1-difluoroethoxyx)phenyl)amino)carbonyl)-2,6-difluorobenzamide. EMI13.1 M.P. = 199 -201 C. Analysis: Calcd: N, 5.67 Found: N, 5.66 N-(((3,5-Dichloro-4-(2,2-dichloro-1,1-difluoro- ethoxy)phenyl)amino)carbonyl)-2-chlorobenzamide. EMI13.2 M.P. = 2000-2020C. Analysis: Calcd: N, 5.69 Found: N, 5.60 N-(((4-(2-Chloro-1,1,2-trifluoroethoxy)-2,5 -dimethylphenyl)amino)carbonyl)-2-chlorobenzamide. M.P. 157 -159 C Analysis: Calcd: C, 49.67; H, 3.47; N, 6.44 Found: C, 49.40; H, 3.36; N, 6.41 N-(((4-(2-Chloro-1,1,2-trifluoroethoxy)-2,5- -dimethylphenyl)amino)carbonyl)-2-chloro-6-fluorobenzamide. M.P. 1450-1470C Analysis: Calcd: C, 47.70; H, 3.11, N, 6.18 Found C, 47.70; H, 3.09; N, 6.22 N-(((4-(1,1,2,2-Tetrafluoroethoxy)-3,5-dimethyl- phenyl)amino)carbonyl)-2,6-difluorobenzamide. M.P. 1900-1920C Analysis: Calcd: C, 51.43; H, 3.36; N, 6.67 Found: C, 51.30; H, 3.45; N, 6.59 N-(((4-(1,1,2,2-Tetrafluoroethoxy)-3,5-dimethyl- phenyl)amino)carbonyl)-2-chlorobenzamide. M.P. 1650-1670C Analysis: Calcd: C, 51.62; H, 3.61; N, 6.69 Found: C, 51.9; H, 3.60; N, 6.67 N-(((4-(2-Chloro-1,1,2-trifluoroethoxy)-3,5- -dimethylphenyl)amino)carbonyl)-2,6-diflurobenzamide. M.P. 1840-1860C Analysis: Calcd: C, 49.50; H, 3.23; N, 6.42 Found: C, 49.60; H, 3.18; N, 6.38 N-(((4-(2-Chloro-1,1,2-trifluoroethoxy)-3,5- -dimethylphenyl)amino)carbonyl)-2-chlorobenzamide. M.P. 1520-1540C Analysis: Calcd: C, 49.67; , 3.47; N, 6.44 Found: C, 49.70; H, 3.45; N, 6.34 N-( ( (4-(2-Chloro-1,l,2-trifluoroethoxy)-2,5- -dimethylphenyl)amino)carbonyl)-2,6-difluorobenzamide M.P. 1430-1450C Analysis: Calcd: C, 49.50; H, 3.23; N, 6.42 Found: C, 49.50; H, 3.24; N, 6.34 In addition to the above described preparative methods, many of the compounds of this invention can be made by reacting a compound having the formula EMI15.1 wherein all of the substituents are as above defined with a haloalkene as is known in the art. The biological activity of several of these compounds was determined. In the beet armyworm test, cotton leaves were dipped in aqueous suspensions of the chemicals, dried, excised and placed into petri dishes with five second-instar beet armyworm (Spodoptera exigua) larvae. Mortality counts were made five days later. The tobacco budworm test was the same except that five tobacco budworm (Heliothis virescens) larvae were placed onto the treated leaves. The results are summarized below: EMI16.1 Percent Control at Indicated Dosage, ppm Beet Army Worm Test (1) Tobaco Budworm Test (2) Compound Ar 400 100 25 400 100 25 A 2,6-difluorophenyl 100 100 100 100 100 80 B 2-chlorophenyl 100 100 100 100 80 40 (1) Untreated check mortality 0%. (2) Untreated check mortality 27%. Employing the above described preparative and testing methods, the compounds listed in the following table were prepared and tested. The test results, LD90 ppm, indicate the dosage necessary to obtain 90 percent kill of the indicated insect. EMI18.1 LD90, ppm Melting Beet Ex. Point Armys- Tobacco No. R1 R2 R3 R4 Y X1 X2 X3 X4 R C worm Budworm 1 F F H H O H Cl Cl H OCF2CHF2 197-199 1.6 1.6 2 F F H H O H Cl Cl H OCF2CHFCl 176-178 1.2 1.2 3 F F H H O H Cl Cl H OCF2CHFBr 170-172 1.2 2.5 4 F F H H O H Cl Cl H OCF2CHFI 170-172 12.5 5 F F H H O H Cl Cl H OCF2CHCl2 197-199 5.0 25.0 6 F F H H O H Cl Cl H OCF2CH2Cl 188-190 100.0 100.0 7 F F H H O H Cl Cl H OCF2CHBr2 215-217 25.0 400.0 8 F F H H O H Cl Cl H OCFClCHFCl 203-205 1.25 25.0 9 F F H H O H Cl Cl H OCF3 218-220 0.6 12.5 10 F F H H O H Cl Cl H OCF2CF3 224-227 12.5 50.0 11 F F H H O H Cl Cl H SCF2CHFCl 250-260 200.0 > 400.0 LD90, ppm Melting Beet Ex. Point Armys- Tobacco No. R1 R2 R3 R4 Y X1 X2 X3 X4 R C worm Budworm 12 F F H H O H Cl Cl H SCF2CHF2 166-168 3.1 12.5 13 Cl H H H O H Cl Cl H OCF2CHFCl 178-180 5.0 6.2 14 Cl H H H O H Cl Cl H OCF2CHF2 173-175 100.0 25.0 15 Cl H H H O H Cl Cl H OCF2CHFBr 183-185 2.5 10.0 16 Cl H H H O H Cl Cl H OCF2CHFI 171-174 50.0 17 Cl H H H O H Cl Cl H OCF2CHCl2 200-202 6.2 200.0 18 Cl H H H O H Cl Cl H OCF2CHBr2 217-219 25.0 400.0 19 Cl H H H O H Cl Cl H OCF3 203-205 2.5 12.5 20 Cl H H H S H Cl Cl H OCF2CHFCl 137-139 10.0 200.0 21 Cl H H H S H Cl Cl H OCF2CHF2 140-142 400.0 50.0 22 F F H H S H Cl Cl H OCF2CHFCl 149-151 12.5 12.5 23 F F H H S H Cl Cl H OCF2CHF2 166-168 24 F H H H O H Cl Cl H SCF2CHFCl 245-250 > 400.0 > 400.0 25 F H H H O H Cl Cl H OCF2CHFCl 165-167 100.0 25.0 26 F Cl H H O H Cl Cl H OCF2CHF2 EMI20.1 <SEP> LD90, <SEP> ppm <tb> <SEP> Melting <SEP> Beet <tb> Ex. <SEP> Point <SEP> Armys- <SEP> Tobacco <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> R4 <SEP> Y <SEP> X1 <SEP> X2 <SEP> X3 <SEP> X4 <SEP> R <SEP> C <SEP> worm <SEP> Budworm <tb> 27 <SEP> F <SEP> Cl <SEP> H <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHF2 <SEP> 205-207 <SEP> 2.5 <SEP> 5.0 <tb> 28 <SEP> F <SEP> Cl <SEP> H <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHFBr <SEP> 184-186 <SEP> 2.5 <SEP> 5.0 <tb> 29 <SEP> Cl <SEP> Cl <SEP> H <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHF2 <SEP> 217-219 <SEP> 25.0 <SEP> 25.0 <tb> 30 <SEP> Cl <SEP> Cl <SEP> H <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHFCl <SEP> 221-223 <SEP> 6.2 <SEP> 25.0 <tb> 31 <SEP> Cl <SEP> Cl <SEP> H <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHFBr <SEP> 200-202 <SEP> 100.0 <SEP> 12.5 <tb> 32 <SEP> Cl <SEP> Cl <SEP> H <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> SCF2CHF2 <SEP> 213-215 <SEP> 50.0 <SEP> 200.0 <tb> 33 <SEP> F <SEP> F <SEP> CH3 <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHCl2 <SEP> 153-155 <SEP> 100.0 <SEP> < 400.0 <tb> 34 <SEP> F <SEP> F <SEP> CH3 <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHFCl <SEP> 128-130 <SEP> 100.0 <SEP> 50.0 <tb> 35 <SEP> F <SEP> F <SEP> CH3 <SEP> H <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHF2 <SEP> 102-104 <SEP> 100.0 <SEP> 50.0 <tb> <SEP> O <SEP> O <tb> 36 <SEP> F <SEP> F <SEP> -C-C- <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHCl2 <SEP> 194-197 <SEP> 400.0 <SEP> > 400.0 <tb> <SEP> O <SEP> O <tb> 37 <SEP> F <SEP> F <SEP> -C-C- <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHF2 <SEP> 167-169 <SEP> 100.0 <SEP> > 400.0 <tb> <SEP> O <SEP> O <tb> 38 <SEP> F <SEP> F <SEP> -C-C- <SEP> O <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHFCl <SEP> 190-192 <SEP> 400.0 <SEP> 400.0 <tb> 39 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> H <SEP> Br <SEP> Br <SEP> H <SEP> OCF2CHF2 <SEP> 201-203 <SEP> 3.7 <SEP> 10.0 <tb> LD90, ppm Melting Beet Ex. Point Armys- Tobacco No. R1 R2 R3 R4 Y X1 X2 X3 X4 R C worm Budworm 40 CH3 H H H O H Cl Cl H OCF2CHFCl 163-165 > 200.0 41 CH3 CH3 H H O H Cl Cl H OCF2CHFCl 175-177 > 200.0 42 C2H5 C2H5 H H O H Cl Cl H OCF2CHFCl 182-184 100.0 400.0 43 OCH3 H H H O H Cl Cl H OCF2CHCl 156-158 > 400.0 > 400.0 44 OCH3 OCH3 H H O H Cl Cl H OCF2CHFCl 203-206 100.0 25.0 45 OCH(CH3)2 H H H O H Cl Cl H OCF2CHFCl 239-241 > 400.0 > 400.0 46 OCH(CH3)2 H H H O H Cl Cl H OCF2CF2 242-244 > 400.0 < 400.0 47 F F H H O Cl Cl H H OCF2CHFCl 180-182 0.6 2.5 48 F F H H O Cl Cl H H OCF2CHF2 166-169 12.5 49 F F H H O Cl Cl H H OCF2CHFBr 169-171 1.6 1.6 50 F F H H O CH3 CH3 H H OCF2CHFCl 169-171 51 Cl H H H O CH3 CH3 H H OCF2CHFCl 150-152 52 F F H H O CH3 H CH3 H OCF2CHF2 53 F F H H O CH3 H CH3 H OCF2CHFCl 143-145 3.1 54 F F H H O CH3 H CH3 H OCF2CHFBr LD90, ppm Melting Beet Ex. Point Army- Tobacco No. R1 R2 R3 R4 Y X1 X2 X3 X4 R C worm Budworm 55 Cl H H H O CH3 H CH3 H OCF2CHFCl 157-159 12.5 56 F Cl H H O CH3 H CH3 H OCF2CHFCl 145-147 12.5 57 F F H H O CH3 H H CH3 OCF2CHFCl 191-193 58 F F H H O H CH3 CH3 H OCF2CHF2 190-192 3.1 59 F F H H O H CH3 CH3 H OCF2CHFCl 184-186 1.2 1.2 60 F F H H O H CH3 CH3 H OCF2CHFBr 176-178 3.1 3.1 61 Cl H H H O H CH3 CH3 H OCF2CHF2 165-167 12.5 12.5 62 Cl H H H O H CH3 CH3 H OCF2CHFCl 152-154 5.0 12.5 63 Cl H H H O H CH3 CH3 H OCF2CHFBr 147-149 6.2 25.0 64 F Cl H H O H CH3 CH3 H OCF2CHF2 65 F Cl H H O H CH3 CH3 H OCF2CHFCl 66 F Cl H H O H CH3 CH3 H OCF2CHFBr 67 F F H H O H C2H5 C2H5 H OCF2CHFCl 122-124 25.0 25.0 68 F F H H O CH3 CH3 CH3 H OCF2CHF2 69 F F H H O CH3 CH3 CH3 H OCF2CHFCl 152-154 3.1 3.1 LD90, ppm Melting Beet Ex. Point Army- Tobacco No. R1 R2 R3 R4 Y X1 X2 X3 X4 R C worm Budworm 70 F F H H O CH3 CH3 CH3 H OCF2CHFBr 71 F F H H O CH3 CH3 CH3 CH3 OCF2CHF2 72 F F H H O H OCH3 OCH3 H OCF2CHFCl 142-144 10.0 10.0 73 F F H H O CH3 H Cl H OCF2CHF2 74 F F H H O CH3 H Cl H OCF2CHFCl 178-180 75 Cl H H H O CH3 H Cl H OCF2CHFCl 76 Cl H H H O H Cl CH3 H OCF2CHFCl 77 F F H H O H Cl CH3 H OCF2CHFCl 175-177 78 F F H H O CH3 Cl Cl H OCF2CHF2 79 F F H H O CH3 Cl Cl H OCF2CHFCl 190-192 80 Cl H H H O CH3 Cl Cl H OCF2CHFCl 167-169 81 F F H H O CH3 Cl Cl CH3 OCF2CHFCl 240-241 82 F Cl H H O CH3 Cl Cl CH3 OCF2CHFCl 228-229 EMI24.1 <SEP> LD90, <SEP> ppm <tb> <SEP> Beet <tb> Ex. <SEP> Point <SEP> Army- <SEP> Tobacco <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> R4 <SEP> Y <SEP> X1 <SEP> X2 <SEP> X3 <SEP> X4 <SEP> R <SEP> C <SEP> worm <SEP> Budworm <tb> <SEP> O <tb> 83 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> H <SEP> CCH3 <SEP> CH3 <SEP> H <SEP> OCF2CHFCl <SEP> 163-165 <tb> <SEP> O <tb> 84 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> H <SEP> COCH3 <SEP> CH3 <SEP> H <SEP> OCF2CHCl2 <SEP> 153-155 <tb> <SEP> O <tb> 85 <SEP> Cl <SEP> H <SEP> H <SEP> H <SEP> O <SEP> H <SEP> COCH3 <SEP> CH3 <SEP> H <SEP> OCF2CHCl2 <SEP> 143-145 <tb> 86 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> H <SEP> NO2 <SEP> H <SEP> H <SEP> OCF2CHFCl <SEP> 227-228 <tb> 87 <SEP> Cl <SEP> H <SEP> H <SEP> H <SEP> O <SEP> H <SEP> NO2 <SEP> H <SEP> H <SEP> OCF2CHFCl <SEP> 206-208 <tb> 88 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> Cl <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHF2 <tb> 89 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> Cl <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHF2 <tb> 90 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> Cl <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHFCl <tb> 91 <SEP> F <SEP> F <SEP> H <SEP> H <SEP> O <SEP> Cl <SEP> Cl <SEP> Cl <SEP> H <SEP> OCF2CHFBr <tb> In further tests carried out as above, compounds of the following structure gave the indicated results: EMI25.1 EMI25.2 <tb> <SEP> Lug0' <SEP> ppm <tb> <SEP> Beet <SEP> Tobacco <tb> <SEP> Ar <SEP> R <SEP> M.P., <SEP> OC <SEP> Armyworm <SEP> Budworm <tb> <SEP> OCF2CHCl2 <SEP> 189-192 <SEP> 100 <SEP> > 400 <tb> N <SEP> 1C1 <tb> <SEP> C1 <tb> <SEP> C1 <tb> ¸; <SEP> OCF2CHF2 <SEP> 217-219 <SEP> > 400 <SEP> > 400 <tb> E <SEP> L <tb> <SEP> C1 <tb> <SEP> C1 <tb> ¸; <SEP> OCF2CHC12 <SEP> 228-230 <SEP> > 400 <SEP> > 400 <tb> <SEP> Cl <tb> In further embodiments, the compounds of the present invention or compositions containing the same, can be advantageously employed in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, acaricides, herbicides, fungicides or bactericides that are compatible with the compounds of the present invention in the medium selected for application and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use, or as an additament. The compounds in combination can generally be present in the ratio of from 1 to 100 parts of the compound of the present invention with from 100 to 1 parts of the additional compound(s). The compounds of this invention are, or tend to be, slow acting, i.e., they disrupt the molting of the insect, thereby killing it. As a result, some time can pass before the insects are killed. Accordingly, an increased benefit can be obtained by combining the compounds of this invention with quicker acting insecticides such as, for example, organophosphorus compounds, carbamates and pyrethroids. Because of this different mode of action, the compounds of this invention kill or control insects which have, or may be developing, resistance to the more common insecticides and thus they inhibit or delay the development of resistance to such insecticides. Various modifications may be made in the present invention without departing from the spirit or scope thereof and it is understood that we limit ourselves only as defined in the appended claims.

Claims: WE CLAIM: 1. A compound having the formula EMI27.1 wherein Ar is a substituted phenyl, pyridyl, or pyrimidinyl radical wherein the substituents are chloro, bromo, fluoro, C1-C3 alkyl or C1-C3 alkoxy, with the proviso that at least one substituent is positioned ortho to the carbonyl group; R3 and R4 are individually H or C1-C4 alkyl or together they form the group EMI27.2 Y is o or s; X,, X2, X3 and X4 are individually H, halogen, C1-C3 alkyl, C1-C3 alkoxy, alkylcarbonyl, alkoxycarbonyl, C1-C3 alkylthio, NO2, CN or NR5R6 wherein R5 and R6 are H or C1-C3 alkyl with the provisos that at least one of Xl, X2, X3 or X4 is other than H and (a) when three of X1, X2, X3 or X4 are H, the fourth substitution cannot be halogen or alkyl, (b) when X1 and X3 are H, X2 and X4 cannot both be halogen, (c) when X2 and X3 are H, X1 and cannot both be halogen and R is a C1-C4 haloalkyl, haloalkoxy or halpalkylthio group. 2. Compound of Claim 1 having the formula EMI28.1 wherein X1 and X4 are hydrogen and X2 and X3 are halogen. 3. Compound of Claim 2 having the formula EMI28.2 wherein R1 is F or Cl and R2 is H, F or C1. 4. Compound of Claim 3 wherein X2 and X3 are independently F, C1 or Br and R is OCF3, OCF2CHCl2, OCF2CHF2, OCF2CHFC1, OCF2CHFBr, OCF2CHFI, OCFClCHFCl or SCF2CHF2. 5. Compound of Claim 4 wherein R1 and R2 are both F, X2 and X3 are both C1, Y is 0 and R is OCF2CHF2. 6. Compound of Claim 4 wherein R1 and R2 are both F, X2 and X3 are both C1, Y is O and R is OCF2CHFC1. 7. Compound of Claim 4 wherein R1 and R2 are both F, X2 and X3 are both C1, Y is 0 and R is OCF2CHFBr. 8. Compound of Claim 4 wherein R1 is C1, R2 is H, X2 and X3 are both C1, Y is 0 and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 9. Compound of Claim 4 wherein R1 is C1, R2 is F, X2 and X3 are both C1, Y is o and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 10. Compound of Claim 1 having the formula EMI29.1 wherein X1, X2, X3 and X4 are individually H, halogen, C1-C3 alkyl, C1-C3 alkoxy, alkylcarbonyl, alkoxycarbonyl, C1-C3 alkylthio, NO2, CN or NR5R6 wherein R5 and R6 are H or C1-C3 alkyl with the provisos that at least one of Xl, X2, X3 or X4 is other than H and (a) when three of Xl, X2, X3 or X4 are H, the fourth substitution cannot be halogen or alkyl, (b) when X1 and X3 are H, X2 and X4 cannot both be halogen, (c) when X2 and X3 are H, X1 and X4 cannot both be halogen, (d) when X1 and X4 are hydrogen, X2 and X3 cannot both be halogen and R is a C1-C4 haloalkyl, haloalkoxy or haloalkylthio group. 11. Compound of Claim 10 having the formula EMI30.1 wherein R1 is F or C1, R2 is H, F or Cl, X1, X2, X3 and X4 are individually H, halogen, alkyl or alkoxy and R is a C1-C4 haloalkyl, haloalkoxy or haloalkylthio group. 12. Compound of Claim 11 wherein X1, X2, X3 and X4 are individually B, C1, F, Br, CH3 or OCB3 and R is CF3, OCF3, OCF2CHC12, OCF2CHF2, OCF2CHFCl, OCF2CHFBr, OCF2CHFI, OCFClCHFCl or SCF2CHF2. 13. Compound of Claim 12 having the formula EMI30.2 wherein R1 is F or C1, R2 is H, F or C1, X1 is H, Cl or CH3, X2 is H, cl, CH3 or OCH3, X3 is H, C1, CH3 or OCH3 and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 14. Compound of Claim 13 wherein R1 and R2 are both F, X1 and X2 are both Cl, X3 is H and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 15. Compound of Claim 13 wherein R1 and R2 are both F, X1 is H, X2 and X3 are both CH3 and R is OCF2CHFC1. 16. Compound of Claim 13 wherein R1 and R2 are both F, X1 is H, X2 and X3 are both CH3 and R is OCF2CHF2. 17. Compound of Claim 13 wherein R1 and R2 are both F, X1 is H, X2 and X3 are both CH3 and R is OCF2CHFBr. 18. Compound of Claim 13 wherein R1 is Cl, R2 is F, X1 is H, X2 and X3 are both CH3 and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 19. Compound of Claim 13 wherein R1 and R2 are both F, X1 and X3 are both CH3, X2 is H and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 20. Compound of Claim 13 wherein R1 and R2 are both F, X1, X2 and X3 are CH3 and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 21. Compound of Claim 13 wherein X1 is methyl and X2 and X3 are chloro. 22. A compound having the formula EMI31.1 wherein X1, X2, X3 and X4 are independently H, halogen, C1-C3 alkyl, C1-c3 alkoxy, alkylcarbonyl, alkoxycarbonyl, C1-C3 alkylthio, NO2, CN or NR5R6 wherein R5 and R6 are H or C1-C3 alkyl with the provisos that at least one of X1, X2, X3 or X4 is other than H and (a) when 3 of X1, X2, X3 or X4 are H, the fourth substituent cannot be halogen, (b) when X1 and X3 are H, X2 and X4 cannot both be halogen, (c) when X2 and X3 are H, X1 and X4 cannot both be halogen R is a C1-C4 haloalkyl, haloalkoxy or haloalkylthio group and Z is NH2, -N=C=O, EMI32.1 23. Compound of Claim 22 wherein X1 and X4 are hydrogen and X2 and X3 are halogen. 24. Compound of Claim 23 wherein X2 and X3 are independently F, Cl or Br and R is OCF3, OCF2CHCl2, OCF2CHF2, OCF2CHFC1, OCF2CHFBr, OCF2CHFI, OCFClCHFCl or 2CHF2. 25. Compound of Claim 24 wherein X2 and X3 are both C1 and R is OCF2CHF2. 26. Compound of Claim 24 wherein X2 and X3 are both C1 and R is OCF2CHFCl. 27. Compound of Claim 24 wherein X2 and X3 are both C1 and R is OCF2CHFBr. 28. Compound of Claim 22 wherein X1 and X2 are both C1, X3 and X4 are H and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 29. Compound of Claim 22 wherein X1 and X4 are both H, X2 and X3 are both CH3 and R is OCF2CHFC1. 30. Compound of Claim 22 wherein X1 and X4 are H, X2 and X3 are both CH3 and R is OCF2CHF2. 31. Compound of Claim 22 wherein X1 and X4 are H, X2 and X3 are both CH3 and R is OCF2CHFBr. 32. Compound of Claim 22 wherein X1 and X3 are both CH3, X2 and X4 are H and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 33. Compound of Claim 22 wherein X1, X2 and X3 are CH3, X4 is H and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 34. A method for killing and/or controlling insects which comprises applying to the insects, the insect larvae or their habitats an insecticidally effective amount of a compound having the formula EMI33.1 wherein Ar is a substituted phenyl, pyridyl, or pyrimidinyl radical wherein the substituents are chloro, bromo, fluoro, C1-C3 alkyl or C1-C3 alkoxy, with the proviso that at least one substituent is positioned ortho to the carbonyl group; R3 and R4 are individually H or C1-C4 alkyl or together they form the group EMI34.1 Y is O or S; X1, X2, X3 and X4 are individually H, halogen, C1-C3 alkyl, C1-C3 alkoxy, alkylcarbonyl, alkoxycarbonyl, C1-C3 alkylthio, NO2, CN or NR5R6 wherein R5 and R6 are H or C1-C3 alkyl with the provisos that at least one of X1 X2 X3 or X4 is other than H and (a) when three of X1, X2, X3 or X4 are H, the fourth substitution cannot be halogen or alkyl, (b) when X1 and X3 are H, X2 and X4 cannot both be halogen, (c) when X2 and X3 are H, X1 and X4 cannot both be halogen and R is a C1-C4 haloalkyl, haloalkoxy or haloalkylthio group. 35. Method of Claim 34 wherein the compound employed has the formula EMI34.2 wherein R1 is F or C1; R2 is H, F or C1; Y is O or S; X1 is H, C1 or CH3 X2 and X3 are H, C1, CH3 or OCH3 and R is OCF3, OCF2CHF2, OCF2CHFC1, OCF2CHFBr, OCF2CHFI, OCFClCHFCl or SCF2CHF2. 36. Method of Claim 35 wherein Y is O, X2 and X3 are H, C1 or CH3 and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 37. Method of Claim 36 wherein X1 and X2 are both C1, and X3 is H. 38. Method of Claim 36 wherein X2 and X3 are both C1 and X1 is H. 39. Method of Claim 36 wherein X1 and X3 are both CH3, and X2 is H. 40. Method of Claim 36 wherein X2 and X3 are both CR3, and X1 is H. 41. Method of Claim 36 wherein X1, X2 and X3 are all CH3. 42. A composition comprising an insecticidally effective amount of at least one compound having the formula EMI35.1 wherein Ar is a substituted phenyl, pyridyl, or pyrimidinyl radical wherein the substituents are chloro, bromo, fluoro, C1-C3 alkyl or C1-C3 alkoxy, with the proviso that at least one substituent is positioned ortho to the carbonyl group; R3 and R4 are individually H or C1-C4 alkyl or together they form the group EMI36.1 Y is o or S; Xlr X2, X3 and X4 are individually H, halogen, C1-C3 alkyl, C1-C3 alkoxy, alkylcarbonyl, alkoxycarbonyl, C1-C3 alkylthio, NO2, CN or NR5R6 wherein R5 and R6 are H or C1-C3 alkyl with the provisos that at least one of X1, X2, X3 or X4 is other than H and (a) when three of X1, X2, X3 or X4 are H, the fourth substitution cannot be halogen or alkyl, (b) when X1 and X3 are H, X2 and X4 cannot both be halogen, (c) when X2 and X3 are H, X1 and X4 cannot both be halogen and R is a C1-C4 haloalkyl, haloalkoxy or haloalkylthio group. 43. Composition of Claim 42 wherein the compound has the formula EMI36.2 wherein R1 is F or C1; R2 is H, F or Cl; Y is o or S; X1 is H, Cl or C}; X2 and X3 are H, Cl, CH3 or OCH3 and R is OCF3, OCF2CHF2, OCF2CHFC1, OCF2CHFBr, OcF2cHFI, OCFClCHFCl or SCF2CHF2. 44. Composition of Claim 43 wherein Y is O, X2 and X3 are H, C1 or CH3 and and R is OCF2CHF2, OCF2CHFC1 or OCF2CHFBr. 45. Composition of Claim 44 wherein X1 and X2 are both C1, and X3 is H. 46. Composition of Claim 45 wherein X2 and X3 are both C1 and X1 is H. 47. Composition of Claim 45 wherein X1 and X3 are both CH3, and X2 is H. 48. Composition of Claim 45 wherein X2 and X3 are both CH3, and X1 is H. 49. Composition of Claim 45 wherein X1, X2 and X3 are all CH3.

Inventors: RIGTERINK, RAYMOND HENRY, SBRAGIA, RONALD JOSEPH
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1982
Main classification: C07C127
IPC codes: A01N33, C07C335, A01N43, C07C323, A01N37, A01N47, C07C217, C07C325, C07C229, C07C211, C07D213, C07C313, C07C265, C07C275, C07C253, C07C255, C07C67, C07C241, C07C209, C07C205, C07C225, C07D233