INSECTICIDAL SUBSTITUTED BIPHENYL BENZOYLUREAS

The present invention relates to substituted biphenyl benzoylureas, insecticidal compositions thereof, and to a method for controlling insects which damage agricultural or horticultural plants. More specifically the invention relates to selected N-[{(substituted,1'- biphenyl]-4- or 5-yl)amino}carbonyl]-substituted benza- mides which are surprisingly effective in disrupting the normal developmental sequence of foliar feeding insects. ellinga, et al., J. Agr. Food Chem. 2_1(3) (1973), describe the insecticidal activity of substituted biphenyl benzoylureas of formula

wherein R is H, Cl, Br, or NO

Grosscurt, et al., Pest. Bio. Phys. J_3, 249-254 (1980), describe the Ovicidal and Larvicidal Structure- Activity Relationships of Benzoylureas on the House Fly. A compound of the above formula, in which R is Br,- was included in the ovicidal and larvicidal testing.

U.S. patent 4,013,717, issued March 22, 1977, discloses the insecticidal activity of a broad class of benzoyl phenyl urea derivatives, among which are compounds of the general formula

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in which A and B may be, among other things, hydrogen or halogen but are not both hydrogen, and R _p may be a phenyl group substituted with a' wide variety of substituents, among which is a phenyl group optionally substituted with halogen, nitro, cyano or halogenated alkyl.

The present invention provides biphenyl benzoylureas of the general type illustrated above, but in which the phenyl ring attached to urea nitrogen (C-ring of formula I) is substitute-d, the terminal phenyl ring (D-ring of formula I) is optionally substituted, and the C-ring is attached at position 4 or 5. ^• The compounds of this invention exhibit surprisingly high levels of insecticidal activity.

The present invention thus provides compounds represented by the formula

in which A and B are both halogen or one of A and B is hydrogen and the other of A and B is halogen;

R and R ^f are each independently halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, halo- alkylsulfonyl, nitro, or cyano; R" is halogen or alkyl; m is 0 to 3; n is 0 (i.e. R' is hydrogen), 1 to 5 when each R ^» group is halogen, or 1 to 3 when at least one R' group is not hydrogen or halogen; and the biphenyl group is attached at position 4 or 5.

As used in the foregoing description of the substi- tuents and throughout the specification and claims, the term "alkyl", as applied to a substituted group, means a

f OMPI

saturated hydrocarbyl group of one to six carbon atoms, preferably one to four carbon atoms, most preferably one or two carbon atoms. The terms "halo" or "halogen" mean a halogen atom selected from bromine, chlorine and fluorine. Where multiple halogen or alkyl groups are possible they may be the same or different. The term "haloalkyl" alone or as a component of a larger group means an alkyl group of 1 or 2 carbon atoms, preferably one, substituted with at least 1 halogen atom. These definitions prevail unless a contrary intent is expressly set forth.

The compounds of this invention may be prepared by the following schema:

(I) (ID

A substituted benzamide (I) is heated with oxalyl chloride in methylene chloride to produce a substituted benzoylisocyanate (II). Reaction of (II) with a substi¬ tuted biphenyl amine (III) produces the corresponding N-[{ (substituted!! 1,1 '-biphenyl]-3 or -4-yl)araino}carbon- yl]-substituted benzamide (IV). This general procedure

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was described in Wellinga, et al., J. Agr. Food Chem. , 2J., 348 (1973) as Methods A and B and in J. Agr. Food Chem., 21, 993 (1973), both incorporated herein by reference.

The intermediate biphenylamines (III) may be pre¬ pared by the following schema:

(VI)

(III)

A substituted nitroaniline (V) and a substituted benzene are treated with t-butylnitrite and copper powder to produce a substituted nitro biphenyl (VI) . Hydrogeπa- tion of (VI) in methanol (a base such as morpholine may be used) produces the desired biphenyl amine (III). In some cases where R is alkoxy and R' is a trifluoromethyl a mixture of isomers was obtained, i.e. a trifluoromethyl group was in the 2', 3', and 4' positions. In order to separate the isomers the following procedure was used:

*

O-alkyl 3

(III) (VII)

mixture of isomers separation of isomers

(VIII)

isomers separated

The appropriately substituted biphenylamine (III), which contained a mixture of isomers, is treated with phthalic anhydride in acetic acid to produce the substi¬ tuted biphenyl phthalimide (VII). Selective crystalliza _¬ tion of (VII) separated some of the isomers and subsequent treatment of the separated isomers with hydrazine hydrate in ethanol provides the substituted biphenylamine (III) as either a single isoraer or a mixture of the 3- and 4-isoraers.

• The biphenyl araine intermediates (III) which contain a difluoromethoxy in either the R or R' position may be prepared by the reaction of a phenyl substituted nitro-

phenol with chlorodifluoromethane in sodium hydroxide, water and dioxane by the method of T. G. Miller, et al. (J. Org. Chem., 25, 2009 (1960)), subsequent hydrogenation would then produce the desired biphenyl amine intermediate (III).

The following examples illustrate use of the fore¬ going methods of preparation.

Example 1 2-Chloro-N-[{(2-methoxy[ ^' 1,1'-biphenyl]-4-yl)- amino}carbonyljbenzaraide

Step A 2-Methoxy-4-nitro[1,1 '-biphenyl]

During a one hour period 34.6 g (0.34 mole) of t _^ -butylnitrite was added dropwise to a stirred mixture of 37.6 g (0.22 mole) of 2-methoxy-4-nitroaniline, 874.0 g (11.2 moles) of benzene and 37.6 g of copper powder. After complete addition _. the mixture was heated at reflux for approximately 18 hours. The excess benzene was removed by distillation to leave an oil. The oil was purified by column chromatography on silica gel,toluene:- n-heptane (60:40) as eluent, to yield 30.1 g of 2-methoxy- 4-nitro-[ 1,1 '-biphenyl] as a solid, mp 65-66°C.

The nmr and IR spectra were consistent with the proposed structure.

Step B 3-Methoxy-4-phenylaniline

Hydrogenation of 10.0 g (0.044 mole) of 2-methoxy-4- nitroC1,1 '-biphenyl] with 0.2 g of platinum- oxide and 250 ml of methanol in a Parr hydrogenation apparatus produced 8-55. g of 3-methoxy-4-phenylaniline.

The nmr and IR spectra were consistent with the proposed structure.

Step C 2-Chloro-N-[{(2-methoxy[1,1'-biphenyl]-

4-yl)amino}carbonyl]benzamide

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A stirred mixture of 1.54 g (0.01 mole) of 2-chloro- benzoylisocyanate and 2.0 g (0.01 mole) of 3-methoxy-4- phenylaniline in 100 ml of xylenes was heated at reflux for 15 minutes, then allowed to cool to room temperature. A precipitate formed and was collected by filtration and the filter cake rinsed with 25 ml of cold n-heptane to yield 1.84 g of 2-chloro-N-[{(2-methoxy[1,1 '-biphenyl]- 4-yl)amino}carbonyl]benzamide, mp 222-226°C.

Example 2

2,6-Difluoro-N-[{(2-raethoxy-(2'-,3'-,4'-)trifluoro¬ methyl.1,1'-biphenyl]-4-yl)amino}carbonyl]benzamide

Step A 2-Methoxy-4-nitro-(2'-,3'-,4'-)tri- fluororaethyl[1,1'-biphenyl]

By the method of Example 1, Step A, the reaction of

25.0 g (0.15- mole) of 2-methoxy-4-nitroaniline, 25.0 g of copper powder and 21.18 g (0.21 mole) of t^-butylnitrite in

1000 g (6.8 mole) of alpha,alpha,alpha-trifluorotoluene produced 17.0 g of 2-methoxy-4-nitro-(2'-,3'-,4'-)tri- fluoromethylC 1 ,1 '-biphenyl] as a solid, rap 64-74°C (isomer ratio 15:51:34).

The nmr and IR spectra were consistent with the proposed structures.

Step B 3-Methoxy-4-[(2-,3-,4-)trifluoromethyl- phenyl]aniline Hydrogenation of 15.0 g (0.051 mole) of 2-methoxy-4- nitro(2'-,3'-,4'-)trifluoromethyl[ 1,1 '-biphenyl] with 0.2 g of platinum oxide and 250 ml of methanol in a Parr hydrogenation apparatus produced 13.5 g of 3-methoxy-4- [(2-,3-,4-)trifluororaethylphenyl]aniline (isomer ratio

15:52:33 ⁾ .

The nmr and IR spectra were consistent with the proposed structures.

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Step C 2,6-Difluoro-N-[{(2-methoxy-(2'-,3 ^, -,4'-) trifluoromethyl[ 1,1'-biphenyl]-4-yl)amino}- carbonyl]benzamide A mixture of 1.37 g (0.0075 mole) of 2,6-difluoro- benzoyl isocyanate and 2.0 g (0.0075 mole) of 3-methoxy-4- C(2 ^, -,3'-,4'-)trifluoromethylphenyl]aniline in 100 ml of xylene was stirred at room temperature producing a pre¬ cipitate. The solid was collected by filtration and the filter cake rins-ed with cold n-heptane to yield 3.2 g of 2,6-difluoro-N-C{(2-methoxy(2'-,3'-,4'-)trifluoromethyl- [1,1'-biphenyl]-4-yl)amino}carbonyl]benzamide.

Example 3 2,6-Dichloro-N-[{(2',5 ^* -dichloro-2-methoxy- [1,1*-biphenyl]-4-yl)amino}carbonyl]benzamide

Step A 2' ,5'-Dichloro-2-methoxy-4-nitro- [1,1 '.--biphenyl] A mixture of 45.8 g (0.27 mole) of 2-methoxy-4- nitroaniline, 45.8 g of copper powder and 2000 g (13.6 moles) of p-dichlorobenzene was heated at 70-90°C and stirred. After all the p-dichlorobenzene had melted, 421.0 g (0.41 mole) of t_-butylnitrite was added during a one hour period. After complete addition the reaction mixture was stirred at 65°C for approximately 18 hours. The reaction mixture was cooled slightly and diluted with 400 ml of toluene. Excess p-dichlorobenzene was allowed to crystallize and was removed by filtration. The filtrate was passed through silica gel, elution with n-heptane:toluene (1:1); the fractions which contained product were collected and combined. The solvent was- removed to give an oil. The oil was subjected to column chromatography on silica gel, elution with n-hexane:- toluene (9:1), to yield a solid. The solid was purified by recrystallization first from methylcyclohexane then from methanol to yield 16.3 of 2' ,5*-dichloro-2-methoxy-

4-nitro[1 ,1 '-biphenyl] .

Step B 4-(2,5-Dichlorophenyl)-3-methoxyaniline Hydrogenation of 16-3 g (0.055 mole) of 2*,5'- dichloro-2-methoxy-4-nitro[1,1 '-biphenyl] with 0.3 g of platinum oxide, 1.63 g of morpholine and 175.0 ml of methanol in a Parr hydrogenation apparatus produced a dark oil. The oil was purified by column chroraatography to yield 8.3 g of 4-(2,5-dichlorophenyl)-3-methoxyaniline. The nmr and IR spectra were consistent with the proposed structure.

Step C 2,6-Dichloro-N-[{(2' ,5'-dichloro-2-methoxy- [1,1 '-biphenyl]-4-yl)amino}carbonyl]- benzamide

To a stirred solution of 0.84 g (0.0037 mole) of 2,6-dichlorobenzoylisocyanate in 40 ml of xylenes was added 1.0 g (0.0037 mole) of 4-(2,5-dichlorophenyl)- 3-methoxyaniline dissolved in 10 ml of xylenes. The mixture was stirred at room temperature for 2.5 hours then diluted with 60 ml of n-heptane and stirred for an additional half hour. A precipitate formed which was collected by filtration and washed with cold pentane to yield 1.53 g of 2,6-dichloro-N-[{ (2' ,5 ^» -dichloro-2- methoxy-[ 1,1'-biphenyl]-4-yl)amino}carbonyl]benzamide.

Example 4 2,6-Difluoro-N-[{ (2-methoxy[ 1 , 1 ' -biphenyl]-5-yl)- amino}carbonyl]benzamide

Step A 2-Methoxy-5-nitro[1 ,1 '-biphenyl]

By the method of Example 1 Step A, the reaction of 37.63 g (0.22 mole) of 2-raethoxy-5-nitroaniline, 37.63 g of copper powder, and 34.62 g (0.34 mole) of nitrite, in 874.0 g (11.2 mole) of benzene produced 27.2 g of 2-methoxy-5-nitro[1 ,1 '-biphenyl] as a solid, rap

78-80°C.

The nmr and IR spectra were consistent with the proposed structure.

Step B 4-Methoxy-3-phenylaniline

Hydrogenation of 11.5 g (0.05 mole) of 2-raethoxy-5- nitro[1,1 '-biphenyl] with 0.15 g of platinum oxide and 250 ml of methanol in a Parr hydrogenation apparatus produced 10.0 g of 4-meth xy-3-phenylaniline. The nmr and IR spectra were consistent with the proposed structure.

Step C 2,6-Difluoro-N-[{(2-methoxy[1,1'-biphenyl]- 5-yl)aminojcarbonyl]benzamide By the method of Example 2 Step C the reaction of 2.0 g (0.01 mole) of 4-methoxy-3-phenylaniline and 2,6- difluorobenzoylisocyanate in 100 ml of xylenes produced 3.82 g of 2,6-difluoro-N-[{(2-methoxy[1,1'-biphenyl]-5- yl)amino}carbonyl]benzamide. The foregoing compounds, together with other compounds of the invention which were prepared in the manner of the foregoing examples, are shown in Table I. In Table I, the compound of Example 1 above is shown as Compound No. 5, the compound of Example 2 is shown as Compound No. 34, the compound of Example 3 is shown as

Compound No. 47, and the compound of Example 4 is shown as Compound No. 54. Table II sets forth the physical constants for each Compound shown in Table I.

The compounds of this invention were tested by incorporating the compounds into the diet of the test insects, second instar southern armyworms and cabbage loopers. The tests were conducted at rates of 200, 20, and 2 ppm, using ten larvae per replicate and two repli¬ cates per rate. Each test was read one day, three to four days, and seven to ten days after infestation to determine the number dead after at least one molt.

The test media consisted of a microcrystalline cellulose or clay formation (dust) of the test compound mixed with the insect diet. The formulations of each component of the test media and their method of prepara¬ tion are: Composition of Insect Diet parts by weight

Pinto beans 12.90

Wheat germ 5.68 Brewer's dried yeast 3.64

Ascorbic acid 0.37

Methyl paraben 0.23

Sorbic acid 0.11

Sodium benzoate 0.00284 Agar 0.71

Formalin (40?) 0.23

Water 76.13

The agar was dissolved with heating in one-half the water and was brought to a boil. Simultaneously, all other ingredients except the formalin were placed in a blender with remaining water and were reduced to a smooth, homogenous mixture. This mixture was added to the boiling agar. Immediately, the formalin was added with mixing.

The compounds of this invention were formulated as either 20$, 5% or 1% dusts* on a microcrystalline cellulose or clay base. The dusts consisted of the following: ? w/w

Microcrystalline Cellulose Formulation 20? Dust 555 Dust test compound 20 .00 5 .00 microcrystalline cellulo issee 80 .00 95 .00

100 .00 100 .00

Clay Formulation 20% Dust 555 Dust 155 Dust test compound 20 .00 5 - 00 1 .00 base 80 .00 95 .00 99 - 00

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« NAT-

96% Attaclay 255 highly purified sodium ligno- sulfonate (100$) 2% powdered sodium alkylnaphthalene sulfonate (7555)

100.00 100.00 100.00

These formulations were prepared by mixing the active ingredient (i.e. the test compound) with the dry base. Test media containing 200 ppm of the test compound was prepared by making a 'stock solution' from 250 mg of a

2055 dust formulation stirred well with 5 ml of distilled water in a vial. One milliliter of the 'stock solution' was added to 50 ml of warm, i.e molten, insect diet in a plastic petrie dish which was then mixed thoroughly.

After cooling to room temperature, the test media was infested with test larvae and covered.

Lower test rates were prepared by dilution of the

'stock solution' according to the following table: Desired Rate ml of ml of (ppm) 'stock solution' water

20 1 9

2 1 ml of 20 ppm solution 9

The results of diet incorporated testing are summarized in Table III. Included in Table III for comparative purposes are two compounds within the scope of the above mentioned prior art, Compound A (N-[{[1,1- biphenyl]-4-yl)amino}carbonyl]-2,6-dichlorobenzamide) and

B ( -[{(4•-bromo[1 ^■ 1 '-biphenyl)-4-yl)amino}carbonyl]-2,6- dichlorobenzamide. The compounds of the invention were in general vastly superior to Compounds A and B.

The compounds of this invention may be formulated as dusts, e.g. those formulations described- above, or may be formulated as granules, emulsifiable concentrates, wet- table powders, flowable formulations, solutions, . dispersions, suspensions and the like.

In applying the foregoing, chemicals, an effective

insecticidal amount of the active ingredient must be applied. While the application rate will vary widely depending on the choice of the compound, the formulation and mode of application, and the insect species present, a suitable user rate may be in the range of 75 to 4000 g per hectare, preferably 150 g to 3000 g per hectare.

TABLE I

Compound No . B 1 Cl H Cl H 2 Cl H CH ₃ 2-,3-,4-F (17:32:5D ^a

Cl H CH- 2-,3-,4-CF ₃ ⁽ 20:47:33 ⁾

Cl H

^CF 3 2-,3-,4-OCH ₃ (13:33:54)

5 Cl H 0CH ₃ H 6 Cl H OCH 2-F 7 Cl H 0CH- 4-F 8 Cl H OCH 4-C1 9 Cl H OCH, 2-,3-,4-CF ₃ ⁽ 15:52:33 ⁾

10 Cl H 0CH_ 3-,4-CF ₃ (25:75) 1 1 Cl H OCH- 3-,4-CF ₃ (78:22)

12 Cl H OCH- 2-OCH ₃

13 Cl H OCH- 3-OCH ₃ 14 Cl H OCH 4-OCH,

15 Cl H OCH ₃ 2-Cl,5-Cl

16 Cl H 0CHF ₂ 4-OCHF ₂

17 Cl H 0C ₂ H ₅ H

f OMPI

TABLE I (Continued)

Compound No. A B R R' 18 Cl H 0C ₂ H ₅ 2-,3-,4-CF ₃ (15:28:57)

19 Cl H 0C ₂ H ₅ 3-,4-CF ₃ (59:41)

20 F F Cl H 21 F F Cl 2-,3-,4-CF (14:52:34)

22 F F CH 2-,3-,4-F (17:32:51)

23 F F CH ₃ 2-,3-,4-CF ₃ (20:47:33) 24 F F CF ₃ 2-,3-,4-CF ₃ (14:56:30)

25 -F F CF- 2-,3-,4-0CH ₃ (13:33:54)

26 F F 0CH ₃ H 27 F F 0CH ₃ 2-F 28 F F 0CH ₃ 4-F 29 F F OCH 2-,3-,4-F^ (41 :19:40)

30 F F 0CH ₃ 2-C1

31 F F OCH ₃ 3-C1 32 F F 0CH ₃ 4-C1 33 F F OCH 2-,3-,4-CF ₃ (15:52:33)

34 F F 0CH-, 3-,4-CF ₃ (25:75)

35 F F 0CH ₃ 3-,4-CF ₃ (78:22)

36 F F OCH 2-0CH ₃ 37 F F 0CH ₃ 3-OCH ₃ 38 F F OCH 4-OCH ₃ 39 F F OCH„ 2-Cl,5-Cl

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TABLE I (Continued)

Compound No. A B R R'

40 F F 0CHF ₂ 2-,3-,4-CF ₃ (1:58:41)

41 F F 0CHF ₂ 4-0CHF ₂

42 ^' F F 0C ₂ H ₅ H

43 F F 0C ₂ H ₅ 2-,3-,4-CF ₃

⁽ 15:28:57)

44 F F 0C ₂ H ₅ 3-,4-CF ₃ (59:41)

45 Cl Cl CH ₃ 2-,3-,4-CF ₃ ⁽ 20:47:33 ⁾

46 Cl Cl 0CH ₃ 2-Cl,5-Cl

47 Cl Cl 0CH ₃ 3-,4-CF ₃ (25:75)

48 Cl Cl 0CH ₃ 2-0CH ₃

49 Cl Cl OCH 3-OCH ₃

50 Cl Cl 0C ₂ H ₅ 3-,4-CF ₃ (59:41)

51 ^b F F Cl 2-,3-,4-CF ₃ ⁽ 16:51:33 ⁾

OM

TABLE I ( Continued )

Compound No. A B R R'

52 Cl H 0CHF ₂ H

53 F F 0CH ₃ H

54 F F 0CHF ₂ H

a. Numbers in parenthesis are the relative amount of each positional isomer. b. R" = 6-chloro.

- 18 -

TABLE II

Compound Empirical Elemental Analysis No. m.p. (oC) Formula C H

1 175-177 Calcd

^C 20?14 ^C1 2 ^N 2°2 62.35 3-66 Found 61.90 3.60

2 157-162 C ₂₁ H ₁₆ C1F ₂ 0 ₂ Calcd 65.89 4.21

Found 69.09 4.52

3 127-137 Calcd

^C 22 ^H 16 ^C1F 3 ^N 2°2 61.05 3-73

Found 61.28 3-70

4 153-158 Calcd

^C 22 ^H 16 ^C1F 3 ^N 2°3 58.87 3-59 .

Found 59.51 3.46

5 164-166 Calcd

^C 21 ^H 17 ^C1N 2°3 66.23 4.50

Found 66.78 4.22

6 197-198 Calcd 63.25 4.04

^C 21 ^H 16 ^C1FM 2°3

Found 64.26 4.05

7 195-196 C ₂₁ H ₁₆ C1FN ₂ 0 ₃ Calcd 63-25 4.04 Found 63-30 3-75

8 178-179 Calcd 60.74 3.88

^C 21 ^H 16 ^C1 2 ^N 2°3

Found 60.39 4.07

9 130-142 Calcd

^C 22 ^H 16 ^C1F 3 ^N 2°3 58.87 3-59

Found 58.31 3-94

10 155-180 C ₂₂ H ₁₆ C1F ₃ N ₂ 0 ₃ Calcd 58.87 3.59

Found 69-15 3.64

11 155-165 Calcd 58.87 3.59

^C 22 ^H 16 ^C1F 3 ^N 2°3

Found 57.68 3-39

12 155-158 Calcd

^C 22 ^H 19 ^C1N 2°4 64.32 4.66

Found 61.58 4.56

13 130-132d ^C 22 ^H 19 ^C1N 2°4 Calcd 64.32 4.66

Found 66.80 4.79

14 165-170d ^C 22 ^H 19 ^C1N 2°4 Calcd 64.32 4.66

Found 63.39 4.81

15 206-208 Calcd 56.09 3.36

^C 21 ^H 15 ^C1 3 ^N 2°3

Found 57.70 3.20

16 123-125d Calcd

^C 22 ^H 15 ^C1F 4 ^N 2°4 54.73 3.13

Found 54.82 2.99

17 136-137 C ₂₂ H ₁₉ C1N ₂ 0 ₃ Calcd 66.92 4.85

TABLE II (Continued)

Compound Empirical Elemental Analysis No. m.p. (oC) Formula C H

17 Found 67.12 4.89

18 145-155 Calcd

^C 23 ^H 18 ^C1F 3 ^N 2°3 59.69 3-92 Found 57.82 3-98

19 135-148 Calcd

^C 23 ^H 17 ^C1F 3 ^N 2°3 59.81 3.71 Found 59-50 3.97

20 210-212 Calcd

^C 20 ^H 13 ^C1F 2 ^N 2°2 62.11 3.39 Found 64.55. 3.55

21 215-235 C ₂₁ H ₁₂ C1F ₅ N ₂ 0 ₂ Calcd 55.46 2.66 Found 55.90 2.61

22 208-214 Calcd

^C 21 ^H 15 ^F 3 ^N 2°2 65.6 3.93

Found 65.19 4.21

23 215-235 Calcd

^C 22 ^H 15 ^F 5 ^N 2°2 60.83 3-48 Found 60.81 3.41

24 227-240 Calcd

^C 22 ^H 12 ^F 8 ^N 2°2 54.11 2.48 Found 58.17 2.56

25 198-202 Calcd

^C 22 ^H 15 ^F 5 ^N 2°3 58.67 3-36 Found 58.68 3.15

26 207-208 Calcd 4.22

^C 21 ^H 16 ^F 2 ^N 2°3 65.97 Found 66.28 4.37

27 217.5-218.5 Calcd 63-00

^C 21 ^H 15 ^F 3 ^N 2°3 3.77

Found 65.37 4.21

28 201-203 Calcd 63-00

^C 21 ^H 15 ^F 3 ^N 2°3 3.77 Found 62.24 3.47

29 203-205 Calcd 63.00

^C 21 ^H 15 ^F 3 ^N 2°3 ^• 3.77 Found 62.24 3.47

30 225.5-226.5 Calcd 60.52 3.62

^C 21 ^H 15 ^C1F 2 ^N 2°3 Found 60.94 3-97

31 198.5-200 Calcd 60.52 3.62

^C 21 ^H 15 ^C1F 2 ^N 2°3 Found 60.90 3.48

32 221-222 ^C 21 ^H 15 ^C1F 2 ^N 2°3 Calcd 60.52 3-62 Found 60.36 3.49

33 188-205 Calcd 58.67 3-36

^C 22 ^H 15 ^F 5 ^N 2°3 Found 59-56 3.30

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TABLE II (Continued)

Compound Empirical Elemental Analysis

No. m.p. (oC) Formula C H 3 224-234 ^C 22 ^H 15 ^F 5 ^N 2°3 ^{Calcd 58*67 3*36}

Found 59-35 3-27

35 185-190 C ₂₂ H ₁₅ F ₅ N ₂ 0 ₃ Calcd 58.67 3-36

Found 58.79 3.29

36 240-242d ^C 22 ^H 18 ^F 2 ^N 2°4 ^{Calcd 64} * ^{08 4} * ⁴⁰ Found 63.70 4.08

37 191-193 ^C 22 ^H 18 2 ^N 2°4 ^{Calcd 64,08} " ⁴⁰

Found 65.95 4.30

38 218-219 ^C 22 ^H 18 ^F 2 ^N 2°4 ^{CalCd 64*08} ' ⁴⁰

Found 63.90 4.25 39 214-216 C^H^C^F^O Calcd 56.00 3-13

Found 56.49 3-04

40 188-205 C ₂₂ H ₁₃ F ₇ N ₂ 0 ₃ Calcd 54-33 2.69

Found 54.45 2.49

41 175-177d ^C 22 ^H 14 ^F 6 ^N 2°4 ^Calcd 5 -5δ ^' .91 Found 54.69 3-10

42 198-199 ^C 22 ^H 18 ^F 2 ^N 2°3 ^{Calcd 66} ' ^{66 *5δ}

Found 66.31 4.25

43 198-208 C^H^F^^ Calcd 59-49 3-69

Found 60.36 3-79 44 200-210 C^H^F^O Calcd 59.49 3-69

Found 59-79 3-54

45 160-180 C ₂₂ H ₁₅ C1 ₂ F ₃ N ₂ 0 Calcd 56.55 3-24

Found 53-50 2-85

46 184-I87d C^H^Cl^N^ Calcd 52.10 2.91 Found 51-98 2-78

47 197-210 C ₂₂ H ₁₅ C1 ₂ F ₃ N ₂ 0 ₃ Calcd 54.68 3-13

Found 54.22 2.97

48 175-178 ^C 22 ^H 18 ^C1 2 ^N 2°4 ^{Calc 59*34 4} ' ⁰⁷

Found 61.82 4.44 49 143.5-145.5 ^C ₂ 2 ^H 18 ^C1 2 ^N 2°4 ^{Calcd 59*34} * ⁰⁷

Found 56.76 3 _* 96

50 135-160 C ₂₃ H ₁₇ C1 ₂ F ₃ N ₂ 0 ₃ Calcd 55.55 3- 5

TABLE II (Continued)

Compound Empirical Elemental Ana ilysis No. m.p < . (oC) Formula C H

50 Found 54.89 3-27

51 181- -183 Calcd

°_1 ^H 17 ^C1N _°3 66.23 4-50 Found 66.07 4.49

52 160- ■162 Calcd

^C 21 ^H 15 ^ClF 2 ^N -°3 60.51 3-63 Found 62.02 3.73

53 187- •189 Calcd 65.97 4.22

^C 21 ^B 16 ^F 2 ^*, 2°3 Found 65.94 4.41

54 151- .154 ^C 21 ^H lΛ ^N 2°3 Calcd 60.29 3-37

Found 60.02 3-37

TABLE III

Diet Incorporated Screen % Kill (5? Formulation on Clay)

Exposure Insects Tested and Rate

Compound Period SAW (ppm)ι CL (ppm)

No. (days) 200 20 2 200 20 2

1 ^b 1 0 0 0 10 0 0

5 100 100 20 ^e 60 10 0

8 ^' 100 100 80 60 40 10

2 ^b 1 0 0 0 0 0 20

3 ^' 40 40- 0 50 0 20

8 100 100 100 90 40 ^s 20 ^S

3 1 0 0 0 70 20 0

4 100 100 70 100 100 90

8 100 100 100 100 100 90

4 3 40 100 90 0 0 20

7 100 100 100 70 50 20

5° 1 0 0 0 0 0 0

3 0 40 50 10 0 0

8 0 100 100 10 20 ^h 0

6 1 0 0 0 0 0 0

7 90 90 50 10 0 0

7 1 0 0 0 0 0 0

7 100 100 50 10 10 20

8 1 30 0 0 10 0 o ^"

3 80 70 30 70 80 90

8 100 100 100 100 100 100

9 ^C 1 0 0 0 10 0 0

3 100 100 100 60 50 100

8 100 100 100 100 100 100

10 1 0 0 0 20 10 10

4 100 100 100 100 100 90

8 100 100 100 100 100 100

11 1 0 0 10 0 0 10

3 100 0 10 0 0 10

8 100 0 10 ¹ 10 10 10

TABLE III ( Continued )

Diet ; Incorporateid Screen

% Kill (5* Formulation on Clay)

Exposure Insects Tested ^a and Rate

Compound Period SAW (ppm) CL (ppm)

No. (days) 200 20 2 200 20 2

12 1 0 0 0 0 0 0

6 0 10 0 0 0 0

8 ^' 0 10 0 10 0 10

13 1 0 0 0 20 0 10

6 10 0 0 20 0 10

8 10 0 0 20 10 10

14 4 100 30 0 30 0 0

8 100 50 0 80 0 0

15 1 0 0 0 0 0 0

3 70 60 0 0 0 10

8 100 90 40 ^e 40 10 10

16 1 0 0 0 0 ^■ 0 0

3 100 100 60 60 100 70

8 100 100 80 100 100 100

17 ^b 1 0 0 0 0 10 0

3 100 100 90 20 10 0

8 100 100 90 90 60 0

18 1 0 0 0 0 0 0

2 0 0 0 0 0 0

8 100 0 0 100 0 0

19 1 0 0 0 20 10 10

4 100 100 100 100 100 90

8 100 100 100 100 100 100

20 ^b 1 0 0 0 0 0 0

5 100 ^• 100 20 ^e 50 30 0

8 100 100 50 50 40 0

21 1 0 0 0 0 0 0

3 100 90 100 100 70 30

8 100 100 100 .100 90 100

22 ^b 1 0 0 0 0 0 0

f OMPI ^*

TABLE III (Continued)

Diet Incorporate!d Screen % Kill ( 5% Formulation *on Clay)

Exposure Insects Tested ³ and Rate

Compound Period SAW (ppm) CL (ppm)

No. (days) 200 20 2 200 20 2

22 ^b 3 90 40 70 40 0 0

8 100 100 100 80 50 0

23 1 0 0 0 0 0 0

4 100 100 100 90 90 80

8 100 100 100 100 100 100

24 1 0 0 0 30 20 0

4 100 100 100 100 90 80

8 100 100 100 100 100 90

25 ^b 3 90 90 90 0 0 0

_* - 7 100 100 100 40 30 10

26 1 0 0 0 0 0 0 5 100 90 ^j 80 40 ^f 0 o

9 100 100 100 40 ^f 10 10

27 1 0 0 0 0 0 0

6 100 100 100 40 40 0

8 100 100 100 50 60 0

28 1 0 0 0 0 0 0

6 100 100 100 80 10 0

8 100 100 100 90 10 0

29 1 0 0 0 0 0 0

4 100 100 100 90 70 0

8 100 100 100 100 90 0

30 1 0 0 0 0 •0 0

3 100 100 0 0 0 0

8 100 100 50 50 10 0

31 1 0 0 0 0 0 0

3 100 100 100 60 90 90

8 100 100 100 100 100 100

32 1 0 0 0 0 0 0

3 100 90 60 90 100 10

f OMPI T*ΠF

TABLE III (Continued)

Diet Incorporated Screen

% Kill (555 Formulation on Clay)

Exposure Insects Tested ³ and Rate

Compound Period SAW (ppm ) CL (ppm)

No. (days) 200 20 2 200 20 2

32 8 100 100 100 100 100 100

33 ^C 1 0 0 0 0 0 0

3 ^' 100 100 30 90 80 30

8 100 100 80 100 100 80

34 ^• 1 0 0 0 30 0 0

3 100 100 100 100 90 _. 70

8 100 100 100 100 100 100

35 1 0 0 0 0 0 0

3 100 100 100 80 100 100

8 100 100 100 100 100 100

36 1 0 0 0 0 0 0

4 40 0 0 0 0 0

8 50 10 0 0 0 0

37 1 0 0 0 0 0 0

4 100 100 100 50 20 . 10

8 100 100 100 80 60 30

38 4 100 100 70 40 70 0

8 100 100 90 100 90 90

39 1 0 0 0 0 0 0

6 100 90 30 100 40 0

8 100 90 60 100 50 10

40 1 o ^d 10 0 0

2 90 100 50

4 100 ^d 100 100 100

41 1 0 0 0 0 0 0

3 100 100 90 90 90 60

8 100 100 90 100 90 100

42 ^b 1 0 0 0 0 0 0

4 100 100 80 _. 10 0 0

8 100 100 100 30 0 0

- 26 -

TABLE III (Continued)

Diet Incorporated Screen % Kill ⁽ 556 Formulation on Clay)

Exposure Insects Tested ³ and Rate

Compound Period SAW (ppm) ^" Cf (ppm)

No. (days) 200 20 2 200 20 2

43 1 0 0 0 0 0 0

2 ^• 10 0 0 100 70 70

8' 100 100 100 100 100 100

44 1 0 0 0 20 10 0

4 100 100 30 100 100 80

8 100 100 100 100 100 90

45 1 0 0 0 0 0 0

3 100 100 100 100 80 50

8 100 100 TOO 100 100 100

3 100 10 0 40 0 0

8 100 50 0 90 20 0

47 1 0 0 0 30 20 0

4 100 100 10 90 100 0

8 100 100 70 100 100 60

48 1 0 0 0 0 0 10

6 100 20 0 70 20 10

8 100 30 0 80 20 10

49 1 0 0 0 0 0 0

3 40 60 0 100 40 0

8 100 100 0 100 70 0

50 1 0 0 0 90 0 10

4 100 100 10 90 100 20

8 100 100 70 100 100 20

51 3 90 90 30 90 10 40

7 100 100 60 100 90 60

52° 1 0 0 0 10 0 0

6 80 0 0 100 20 0

9 90 60 10 100 60 0

53° 1 0 0 0 0 0 0

( O

TABLE III ( Continued )

Diet Incorporated Screen

% Kill (55$ Formulation on Clay) g

Exposure Insects Tested and Rate

Compound Period SAW (ppm) CL (ppm)

No. (days) 200 20 2 200 20 2

53° 3 100 80 40 80 20 0

10, 100 100 70 90 50 10

54° 1 0 0 0 0 0 0

6 100 100 60 100 70 10

9 100 100 70 100 100 40

A 1 0 0 0 0 0 - 0

3 90 30 0 0 0 0

8 100 100 0 30 0 0

B 1 0 0 0 0 0 0

3 0 0 0 0 0 0

8 0 20 0 0 20 0

a . Insect Species : SAW = Southern armyworm (Spodoptera eridania) ; CL s Cabbage looper (Trichoplusia ni). b. 55? Formulation on microcrystalline cellulose. c. 20 Formulation on microcrystalline cellulose. d. ^* [ % formulation on clay. e. SAW moribund with mottled appearance of larvae. f. CL moribund with browning of bodies. g. CL moribund with patchy browning of bodies, h. CL moribund with black spots on bodies. i. Moribund with small, unhealthy larvae. j. Head detached from body. k. Moribund with two headed larvae.