CA2093351A1 - Semicarbazone arthropodicides - Google Patents

Abstract

Arthropodicidally active compounds of formula (I) including all geometric and stereoisomers and agriculturally suitable salts thereof, wherein J, X, R1, R6, Z and n are defined in the text; compositions containing them and use of said compounds to control arthropods.

Description

W092/~76 PCT/US91/07~1 TITTF
SEMICARBAZONE ARTHROPODICIDES
R~CKGROUND OF T~ TNVF.NTION
F;el~ of ~he Invent;on This invention concerns arthropodicidal semicarbazones and their use to control arthropods.
St~te of the Art U.S. 3,885,042 discloses insecticidal benzylidene semicarbazides. U.S. 3,712,914 and U.S. 3,753,680 disclose arylidene semicarbazides as herbicides. U.S.
3,274,115 discloses semicarbazides as germicides while U.S. 3,558,654 discloses semicarbazone and thiosemicarbazone quaternary salts as neuromuscular blocking agents. DE 3,624,349 discloses substituted arylhydrazones as pesticides. Japan Kokai 83/189,192 discloses organic phosphoric acid esters as insecticides.
WO 90/07495 discloses substituted semicarbazone arthropodicides. U.S. 4,547,524 discloses benzoyl hydrazone derivatives as insecticides. EP 3,913 discloses substituted benzophenone hydrazones as insecticides. EP 254,461 discloses N-substituted hydrazones as insecticides. U.S. 3,753,680 discloses arylidene semicarbazones as herbicides. FR 1,455,835 discloses herbicidal hydrazine compositions. EP 34,010 discloses substituted thiosemicarbazones as plant growth regulators. Japan Kokai 87/45,570 discloses aryl and heterocyclic semicarbazones as herbicides.
SU~MA~Y OF T~ INV~NTION
The invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides in both W O 92/06076 ~ ~ PC~r/US91/07091 ~9~ 2 agronomic and nonagronomic environments. The compounds are:

J-~N--~(Rl)n I

wherein J is selected from the group A-Q A-Q

(R3)m ~ R5 ~ m~ N = ~ 7 R2 ~2 J-l A-Q A-Q

(R3)m ~ R8 R~ ' m~ R8 R

J-3 J~

W O 92/06076 PC~r/US91/07091 G ~ ~ G
I ~R7 8 ~ N

J-~ J-6 A is a single bond or selected from the group C1-C3 alkylene and C3-C6 cycloalkylene each of which is optionally substituted with 1 or 2 R9;
G is C1-C2 alkylene optionally substituted with 1 or 2 CH3;
Q is selected from the group H, R9, phenyl optionally substituted with (R4)p, thienyl optionally substituted with W, pyridinyl optionally substituted with W, C1-C6 alkyl optionally substituted with R9 and C3-C6 cycloalkyl optionally substituted with R9;
provided that when J is J-1 and A is methylene, then Q is other than H;
X is selected from the group O and S;
Z is selected from the group N and CH;
R1, R2, R3 and R4 are independently selected from the group halogen, CN, SCN, R10, OR10, S(O)qR10r OSO2R10, C(O)R10, CO2R10, C(o)N(Rlo)Rll SO2N(R1O)R11 and N(RlO)Rll; and when m, n or p is

2, ~R1)2, (R3)2, (R4)2 or R2 and R3 when attached to adjacent atoms can be taken together as OCH2O, OCF2O, OCH2CH2O, OCH2C(CH3)2O or OCF2CF2O to form a cyclic bridge; provided that when R2 is Cl then R3 is other than Cl;

W092/06076 ~ ~ PCT/US91/07091 9~ 4 R5 and R6 are independently selected from the group H, Cl-C6 alkyl, C2-C6 alkoxyalkyl, CHO, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 haloalkylcarbonyl, C1-C6 alkylthio, C1-C6 haloalkylthio, R12oC(o)N(R13)S-, R15(R14)NS- and benzyl optionally substituted with W;
R7 is selected from the group H, C1-C6 alkyl,Cl-C6 haloalkyl and phenyl optionally substituted with W;
R8 is selected from the group H, C1-C3 alkyl, CO2R10 and C(O)N(R10)R11;
R9 is selected from the group halogen, NO2, CN, Cl-C3 alkyl, Cl-C3 haloalkyl, OH, OR10, S(O)qR10, N(H)Rll, N(R10)Rll and CO2R10;
R10 is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C3-C4 alkynyl, C3-C4 haloalkynyl, C2-C6 alkoY.yalkyl, C2-C6 alkylthioalkyl, C2-C6 cyanoalkyl, C3-C6 alkoxycarbonyl alkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 alkylcycloalkyl, C4-C7 haloalkylcycloalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benzyl substituent(s) are 1 to 3 substituents independently selected from W;
R11 is selected from the group H and C1-C4 alkyl;
R12 and R13 are independently selected from C1-C6 alkyl;
R14 and R15 are independently selected from Cl-C4 alkyl; or R14 and R15 when attached to the same atom can be taken together as (CH2)s or CH2CH2OCH2CH2;

W092/0~76 PCT/US91/07091 - 5 2093351~

W is selected from the group halogen, CN, NO2, Cl-C2 alkyl, Cl-C2 haloalkyl, Cl-C2 alkoxy, Cl-C2 haloalkoxy, Cl-C3 alkylthio, Cl-C2 haloalkylthio, Cl-C2 alkylsulfonyl, and Cl-C2 haloalkylsulfonyl;
m is 0 to 2;
n is l to 2;
p is 0 to 2; and q is 0 to 2.

In the above recitations, the term "alkyl", used either alone or in compound words such as "alkythio" or haloalkyl", denotes straight chain or branched alkyl such as methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl, hexyl isomers. Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy or hexyloxy isomers. Alkenyl denotes straight chain or branched alkenes such as vinyl, l-propenyl, 2-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkynyl denotes straight chain or branched alkynes such as ethynyl, l-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers. Alkylthio denotes mehtylthio, ethylthio and the different propylthio, butylthio, pentylthio and hexylthio isomers.
Alkylsulfinyl, alkylsulfonyl, alkylamino, and the like, are defined analogously to the above examples.
Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. ~urther, when used in compound words such as "haloalkyl" said alkyl can be partially or fully W092/0~76 ~ PCT/US91/07091 ~,' ~ ~ 6 q~
substituted with halogen atoms, which can be the same or different. Examples of haloalkyl include CH2CH2F, CF2CF3 and CH2CHFCl. The terms "halocycloalkyl" haloalkenyl"
and "haloalkynyl" are defined analogously to the term "haloalkyl".
The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from l to 7. For example, Cl-C3 alkysulfonyl would designate methylsulfonyl through propylsulfonyl; C2 alkoxyalkoxy designates OCH2OCH3; C4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including OCH2OCH2CH2CH3 and OCH2CH2OCH2CH3; C2 cyanoalkyl designates CH2CN and C3 cyanoalkyl designates CH2CH2CN and CH(CN)CH3; C2 alkylcarbonyl designates C(O)CH3 and C4 alkylcarbonyl includes C(O)CH2CH2CH3 and C(O)CH(CH3)2; and as a final eYample, C3 alkoY.ycarbonylalkyl designates CH2CO2CH3 and C4 alkoxycarbonylalkyl includes CH2CH2CO2CH3, CH2CO2CH2CH3 and CH(CH3)CO2CH3.
Preferred compounds A are those compounds of Formula I wherein:
A is selected from the group Cl-C3 alkylene and C3-C6 cycloalkylene each of which is optionally substituted with l or 2 R9;
Q is selected from the grovp CO2Rl0, phenyl optionally substituted with (R4)p, Cl-C6 alkyl optionally substituted w th R9 and C3-C6 cycloalkyl optionally substituted with R9;
X is O;
Rl, R2, R3 and R4 are independently selected from the group halogen, CN, RlO, ORlO, S(O)qRl0 and OSO2RlO;

W092/0~76 PCT/US91/07091 7 2093`;3~1 R5 and ~6 are independently selected from the group H, Cl-C2 alkyl, C2-C3 alkylcarbonyl and C2-C3 alkoxycarbonyl;
R7 is selected from the group H and CH3;
R8 is H;
R9 is selected from the group halogen, CN, Cl-C3 alkyl, Cl-C3 haloalkyl, ORlO, S(O)qRl0 and C02R10;
RlO is selected from the group Cl-C3 alkyl and Cl-C3 haloalkyl;
Rll is selected from the group H or CH3;
is selected from the group halogen, CN, N02, Cl-C2 alkyl, Cl-C2 haloalkyl, Cl-C2 alkoxy, Cl-C2 haloalkoY.y, Cl-C2 alkylthio, Cl-C2 haloalkylthio, Cl-C2 alkylsulfonyl and Cl-C2 haloalkylsulfonyl;
m is 0 or l;
n is l with Rl in the para-position;
p is 0 or l; and q is 0 or 2.
Preferred compounds B are those of Preferred A
wherein J is J-l. Preferred compounds C are those of Preferred A wherein J is J-2. Preferred compounds D are those of Preferred A wherein J is J-3. Preferred compounds E are those of Preferred A wherein J is J-4.
Preferred compounds F are those of Preferred A wherein J
is J-5. Preferred compounds G are those of Preferred A
wherein J is J-6. Preferred compot~nds H are those compounds of Formula I wherein A is Cl-C2 alkylene optionally substituted with l or 2 methyl groups.

W092/0~76 ~ ~ PCT/US91/07091 ~ ~ 8 Specifically preferred for ~iological activity and ease of synthesis is the compound of Preferred B which i s :
2-~2-phenyl-l-[3-trifluoromethyl)phenyl]-ethylidene]-N-[4-(trifluoromethoxy)phenyl]-hydrazine carboxamide.

DF.TAIT.S OF T~F INV~.~TION
Compounds of Formula I (J-l) can be prepared from ketones of Formula II ~y a two-step process whereby the Formula II compound is condensed with hydrazine and then reacted with a suitably substituted aryl isocyanate of Formula IV. Procedures for the condensation of hydrazine with ketones are well known. For the purposes of this invention, combination of the Formula II ketone with l to 2 equivalents of hydrazine hydrate in an alcoholic solvent such as methanol, ethanol or propanol at the refluY. temperature of the solvent affords the intermediate hydrazones of Formula III. Subsequent reaction of the Formula III hydrazone with an equimolar amount of an aryl isocyanate affords the Formula I
semicarbazones, typically as high melting solids.
SC~

R2 ,A ~ N-NH2 A~ EtO~ ~ ~\R2 II III

~I + ~ ~ NCO I(J-1) ~Rl) Ketones of Formula II are either known in the art or are available via procedures analogous to known ones.
For example, addition of an aryl magnesium or aryl lithium derivative to an optionally substituted phenyl acetaldehyde affords an intermediate alcohol VI which is then readily oxidized to the Formula II ketone (Schem~e 2). Alternatively, alkylation of a trimethylsilylcyano-hydrin (Formula VIII) with a benzyl halide followed by conversion of the trimethylsilylcyanohydrin group to the ketone is a useful method for synthesis of the Formula II
compounds (Scheme 3).

~C~MF. 2 R2 nB~ ~ o~d, (R3)m(R4)p R2 IV V VI

~ ;' ' 10 5~ ~C~M~ 3 CN
R2 ~ CHO TMSCN ~ O~MS

~3)m R2 VII V~I
(R4) ' I ~ ~ ~ (A=C~) lX X
Compounds of the Formula I (J-2) can be prepared in a conventional three-step process whereby Formula XI
esters are saponified, con~erted to the acid chloride and reacted with an appropriately substituted aniline or pyridine. Scheme 3A illustrates this method.

W092/~76 PCT/US91/07091 .~C~MF 3A

I l)NaOH,CH3OH,H2O, (R3)m ~ N-A~ Q 2)SO~ I(J-2) N ~ R7 Et ~ O (Rl~n XI

Formula XI compounds can be prepared by the reaction of Formula XII hydrazines with esters of the Formula XIII. The reaction can be conducted in the presence or the absence of an acid or base in an unreactive solvent system such as methanol, ethanol, methylene chloride, chloroform, tetrahydrofuran and dioxane, but not limited l~ to these. The temperature of the reaction can be varied from 0C to the reflux temperature of the particular solvent. The reaction is usually complete in 24 h.
Scheme 4 illustrates this transformation.
SC~MF 4 O

,A- Q EtO ~ ~ XI

XII XIII

W092/0~76 ~ 12 PCT/US91/07~1 Compounds of the Formula XII can be prepared by the reaction of Formula XIV derivatives with the reagent 0-(2,~-dinitrophenyl)hydroxylamine (XV) in the presence of a base such as sodium carbonate, sodium bicarbonate or potassium carbonate in a nonreactive solvent such as, but not limited to, dimethylformamide, dimethylsulfoxide, tetrahydrofuran and dioxane. The reaction temperature can vary from 0C to 100C with 25C being preferred.
The reaction is usually complete in 24 h. This procedure is analogous to that described in J. Med. Chem., 1984, 27, 1103. Scheme 5 illustrates these transformations.
SC~MF 5 (R3)m ~ + ~ ~F

xrv xv Compounds of the Formula XIV can be prepared by a two-step process whereby Formula XVI compounds are reacted with appropriately-substituted amines of Formula X~I in the presence of a base such as sodium- or potassium carbonate in a solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and the like. The temperature of the reaction can vary from about 25C to 150C and the reaction is usually complete in 48 h. In the subsequent step, the ortho-nitro substituent can be removed by hydrogenation and reducti~e diazotization ~Tetrahedron Lett. 1989, 929). For further W092/~76 PCT/US91/07091 - 13 2~93351 references on this transformation see March, Advanced Org. Chem., 1985, 646. Scheme 6 illustrates these transformations.
.~C~F~ 6 (R3)m~ DMF m--~N,2A Q
~ I
X~ g~I X~III
H2,Pd;
NaN02, H2S04;
Cu,EtOH

One skilled in the art will recognize Formula XVII
compounds as substituted amines of which the preparations are well documented in the literature (J. Chem. Soc., Chem. Commun. 1987, 897; Synth. Commun. 1980, 10, 107).
Compounds of Formula I (J-3) can be prepared by the reaction of tri- and tetravalent metal species such as titanium, silicon, tin and the like in combination with a reducing agent such as sodium, lithium, or zinc borohydride, lithium aluminum hydride and the like with compounds of Formula I (J-l) as illustrated in Scheme 7.
Literature disclosure of analogous reactions can be found in J. Orç. Chem., 1987, 54, 3750, and Synthesis, 1980, 695. Typical reactions involve the addition of 1 equivalent of a compound of Formula I (J-1) to a solution of 1.1 to 4 equivalents of titanium tetrachloride, with 092/~76 ~ PCT/US9l/07091 c~
~9~ 14 1.5 to 2.5 equivalents being preferred, and 2.1 to 6 equivalents of sodium borohydride with 3.5-4.5 equivalents being preferred.
Conventional organic solvents such as ether, tetrahydrofuran, dimethoxyethane, methylene chloride and chloroform can be used with 1,2-dimethyoxyethane being preferred. The reaction can be conducted at temperatures ranging from -70C to 50C with -10C to 30C being preferred. The reaction time can be 0.1 hour to 48 hours with 2 to 4 hours being preferred.
SC~FMF 7 ~ ~4 (R3)m ~ ,A-Q ' I(J-3) N ~

H~N~o I(J-1) Z ~

(Rl)n Compounds of the Formula I (;r-4) can be prepared from Formula I (J-2) deri~atives ln an analogous fashion as that described for Formula I (J-3~ compounds. Scheme 8 illustrates this method.

~C~MF 8 20933 (R3)m ~ ~ A-Q ' I(J-4) N~R7 H~N

I(J-2) Z ~
(Rl)n Compounds of the Formula I (J-5) can be prepared in an analogous fashion as described for the preparation of Formula I (J-2) deri~ati~es. Scheme 9 illustrates these transformations.

W092/06076 ~ PCT/US9l/07~1 ~ 16 q"Q~
.C~C~F.MF'. 9 (R3)m ~ ~ ~ H2N- ~ NOz B2CO3(B3~ ~ NH2 2~ ~V ~X O

o X~II

l)NaOH,CH30H,H2O, ~

I(J-5) ' (R3)m ~ N

3)H2N

Z I ~J C02Et XVIII
(Rl)n Formula XX compounds can be prepared by the reaction of Formula XXI derivatives with metal hydride reducing agents such as 7inc borohydride, lithium borohydride, sodium borohydride, lithium aluminum hydride and the like in conventional organic solvents such as ether, tetrahydrofuran, dimethoxyethane and dioxane. The reaction can be conducted at temperatures from -78C to the reflux temperature of the particular solvent. The 17 209~33~1 reaction is usually complete in 48 h. Scheme 10 illustrates this method.
.':;CE~F.MF~ 1 0 G Rbd~g (R3)m ~ Y Q Ag~t P XX

a~
One skilled in the art will recognize Formula XXI
derivatives to be indoles and dihydroquinolines of which the preparations are well documented in the literature (J. Med. Chem., 1984, 1439).
Compounds of the Formula I (J-6) can be prepared from Formula I (J-5) derivatives by an analogous procedure as described for Formula I (J-3) compounds.
Scheme 11 illustrates this method.
~;C~F.MF 1 1 (R3)m ~ G Q

N R7 ~4 ~ ~ I(J-6) N O
~' Z ,\
(Rl)n Compounds of Formula I, where R6 is other than H, can be prepared from compounds of Formula XXI (i.e., W092/~076 ~ PCT/US91/07091 ~ 9~ 18 q~
compounds of Formula I where R6 is H) by the reaction with electrophiles R6-L (where L is a leaving group such as Cl, Br, I, alkylsulfonate or arylsulfonate). Useful electrophiles include alkyl halides, such as methyl iodide, dialkylsulfates, such as dimethylsulfate, acyl halides, such as acetyl chloride and alkylchloroformates, such as ethyl chloroformate. The reaction is typically run in polar organic solvents such as tetrahydrofuran and dimethylformamide, and in the presence of a strong base, examples of which include sodium hydride, potassium hydride and potassium t-butoxide. For compounds of Formula XXI containing more than one free NH group, protecting groups may be required to achieve the desired N-substitution. This reaction is illustrated in Scheme 12.
SCE~F.MF. 1~

Il ~ (R )n R6L, 11 ~ (R )n J-~N ~ ~ BaYe 16 ~ Z

XXI

The following Example illustrates the invention.

W092/0~76 PCT/US91/07091 24~33,51 F~xz~IpT~F~ 1 rl- (3-Chlorophenyl~-~-phe~ylethyl;~enel-N-r4-(tri-fllloro~et~yl~phe~yll ~y~r~ 7; nec~ rhox~m; ~e Step A: 2-Phenyl-1-~3-chlorophenyl)ethanone To a solution of 3-bromochlorobenzene ~15 g, 78.3 - 10 mmol) in 150 ml of dry tetrahydrofuran was added 2.5 M
n-butyllithium in hexane ~31.4 ml, 78.3 mmol) dropwise at -78C. A white precipitate crystallized out of the reaction mixture. The reaction was warmed to -20C at which point the precipitate went into solution. To the reaction was then added phenylacetaldehyde ~9.4 g, 78.3 mmol) in 30 ml of dry tetrahydrofuran at -25C. The reaction was then gradually warmed to room temperature and partitioned between ether and 5% aqueous sodium bicarbonate. The ether extracts were then dried over magnesium sulfate and concentrated to 18.86 g of a yellow oil which was purified by chromatography on silica gel (2.5% ethyl acetate in hexane) to afford 10.68 g of a yellow oil, which was confirmed by proton NMR to be 1-~3-chlorophenyl)benzeneethanol.
To a solution of 1-(3-chlorophenyl)benzeneethanol (9.44 g, 40.6 mmol) in 150 ml of methylene chloride was added pyridinium chlorochromate (13.1 g, 60.9 mmol) and the mixture was stirred under nitrogen o~ernight. After this time, the reaction was diluted with 250 ml of ether, filtered through magnesium sulfate and concentrated to 9.34 g of a brown oil. Chromatography on silica gel (10%
ethyl acetate in hexane) aff~rded 8.23 g of the title compound as a yellow solid.
1H NMR (CDC13): ~ 4.25 (s, 2H), 7.2-7.6 (m, 7H), 7.85 (d, lH), 7.97 (s, lH).

W092/06076 ~ PCT/US91/07091 ~ ~ 20 Step B: [1-(3-chlorophenyl-2-phenylethylidene~-N-[4-(trifluoromethyl)phenyl~hydrazine-carboxamide To a solution of the ketone from Step A (2.0 g, 8.7 mmol) in 20 ml of ethanol was added hydrazine hydrate (0.51 ml, 10.4 mmol) and the mixture was heated at reflux under nitrogen overnight. The reaction was then concentrated and partitioned between ether and 5% aqueous sodium bicarbonate. The ether eY.tracts were washed with water, dried over magnesium sulfate and concentrated to 1.86 g of a dark yellow oil. To a mixture of 0.93 g of this oil (3.8 mmol) in 15 ml of tetrahydrofuran was added

4-trifluoromethylphenylisocyanate (0.71 g, 3.8 mmol) and the reaction was stirred under nitrogen for 72 hours.
The reaction was then concentrated and the residue triturated with ether to afford 0.87 g of the title compound as a white solid, mp 225-229C.
H NMR (CDCl3): ~ 4.05 (s, 2H), 7.1-7.5 (m, 7H), 7.55 (d, 2H), 7.65 (d, 2H), 7.78 (bs, lH), 8.08 (s, lH), 8.42 (s, lH).

By the general procedures described herein, or obvious modifications thereof, the compounds of Tables 1 through 12 can be prepared. In the Table Key, nPr is n-propyl, iPr is isopropyl and cPr is cyclopropyl.

21 20933~-fl K~Y FOR TART.~S 1 TO 1 l ~Rl J C ~ N

H

T~hle GroUP J

(a) a J-l (A=CH2, Q=Me, R5-H) (a) b J-1 (A=CH2, Q=nPr, R5=H) 1(a) c J-1 (A=CH2, Q=iPr, R5~H) 2(b) a J-1 (A=CH2, Q=CO2Me, R5=H) 2(b) b J-1 (A=CH2, Q=Ph, R5=H) 2(b) c J-1 (A-CH2, Q=4-F-Ph, R5CH) 2(b) d J-1 (A=CH2, Q=g-Cl-Ph, R5=H) 2(b) e J-1 (A=CH2, Q=4-CF3-Ph, R5=H) 2(b) f J-1 (A=CH2, Q=4-OCF2H-Ph, R5=H) 2(b) g J-1 (A=CH2, Q=4-OCF3-Ph, R5eH) 2(b) h J-1 (A=CH2, Q=4-Me-Ph, R5=H) 2(b) i J-1 (A=cPr, Q=Me, R5=H) 2(b) j J-1 (A=cPr, Q=nPr, R5=H) 2(b) k J-1 (A=cPr, Q=iPr, R5=H) 2(b) 1 J-1 (A=cPr, Q=CO2Me, R5=H) 2(b) m J-1 (A=cPr, Q=Ph, R5=H) 2(b) n J-1 (A=cPr, Q=4-F-Ph, R5=H) 2(b) O J-1 (A-cPr, Q=4-Cl-Ph, R5=H) W092/~76 ~ ~ PCT/US91/07~1 9~
~ 22 T~hle Grol~ J

2(b) p J-l (A=cPr, Q=4-CF3-Ph, R5eH) 2(b) q J-1 (A=cPr, Q-4-OCF2H-Ph, R5CH) 2(b) r J-l (A=cPr, Q~4-OCF3-Ph, R5CH) 2(b) s J-l (A=cPr, Q=4-Me-Ph, R5CH) 3(c) a J-2 (A=CH2, Q=Me, R3=H) 3(c) b J-2 (A=CH2, Q=nPr, R3CH) 3(c) c J-2 (A=CH2, Q=iPr, R3eH) 3(c) d J-2 (A=CH2, Q=CO2Me, R3CH) 3(c) e J-2 (A=CH2, Q=Ph, R3CH) 3(C) f J-2 (A=CH2, Q=4-F-Ph, R3=H) 3(C) g J-2 (A=CH2, Q=4-Cl-Ph, R3=H) 3(c) h J-2 (A=cPr, Q=Me, R3=H) 3(c) i J-2 (A=cPr, Q=nPr, R3eH) 3(C) j J-2 (A=cPr, Q=iPr, R3=H) 3(c) k J-2 (A=cPr, Q=CO2Me, R3=H) 3(c) 1 J-2 (A=cPr, Q=Ph, R3=H) 3(c) m J-2 (A=cPr, Q=4-F-Ph, R3=H) 3(c) n J-2 (A=cPr, Q=4-Cl-Ph, R3=H) 4(d) a J-3 (A=CH2, Q=Me, R3=H, R5eH) 4(d) b J-3 (A=CH2, Q=nPr, R3=H, R5=H) 4(d) c J-3 (A=CH2, Q=iPr, R3=H, R5~H) 4(d) d J-3 (A=CH2, Q=CO2Me, R3=H, R5=H) 4(d) e J-3 (A=CH2, Q=Ph, R3=H, R5=H) 4(d) f J-3 (A=CH2, Q=-l-F-Ph, R3=H, R5=H) 4(d) g J-3 (A=CH2, Q=4-Cl-Ph, R3=H, R5=H) 4(d) h J-3 (A=cPr, Q=~e, R3=H, R5=H) 4(d) i J-3 (A=cPr, Q=nPr, R3=H, R5=H) 4(d) j J-3 (A=cPr, Q--iPr, R3=H, R5=H) 4(d) k J-3 (A=cPr, Q=CO2Me, R3=H, R5=H) 4(d) 1 J-3 (A=cPr, Q=Ph, R3=H, R5=H) 4(d) m J-3 (A=cPr, Q=4-F-Ph, R3=H, R5=H) W 0 92/06076 23 2~3 3 PCI/US91/07091 T~hle Grol~ J

4(d) n J-3 (A=cPr, Q=4-Cl-Ph, R3CH, R5=H)

5(e) a J-4 (A=CH2, Q=Me, R3eH, R8~H
5(e) b J-4 (A=CH2, Q=nPr, R3GH, R8eH) 5(e) c J-4 (A'CH2, Q=iPr, R3GH, R8~H) 5(e) d J-4 (AeCH2, Q=C02Me, R3eH, R8eH) 5(e) e J-4 (A=CH2, Q=Ph, R3eH, R8-H) s(e) f J-4 (A=CH2, QG4-F-Ph, R3eH, R8=H) s(e) g J-4 (AeCH2, Q=4-C1-Ph, R3eH, R8=H) 5(e) h J-4 (AGcPr, Q~Me, R3eH, R8eH) 5(e) i J-4 (A=cPr, Q=nPr, R3eH, R8-H) s(e) j J-4 (A=cPr, Q=iPr, R3eH, R8=H) 5(e) k J-4 (A=cPr, Q=C02Me, R3=H, R8=H) 5(e) 1 J-4 (A=cPr, Q=Ph, R3-H, R8=H) 5(e) m J-4 (A=cPr, Q=4-F-Ph, R3eH, R8=H) 5(e) n J-4 (A=cPr, Q=4-Cl-Ph, R3=H, R8CH)

6 (f) a J-5 (G=CH2, Q=Me) 6 (f) b J-5 (GeCH2, Q=nPr) 6 (f) c J-5 (G=CH2, Q=iPr) 6 (f) d J-5 (G=CH2, Q=C02Me) 6 (f) e J-5 (G=CH2, Q=Ph) 6 (f) f J-5 (G=CH2, Q=4-F-Ph) 6 (f) g J-5 (G=CH2, Q=4-Cl-Ph) 6 (f) h J-5 (G=CH2CH2, Q=Me) 6 (f) i J-5 (G=CH2CH2, Q=nPr) 6 (f) j J-5 (G=CH2CH2, Q=iPr) 6 (f) k J-5 (G=CH2CH2, Q=C02Me) 6 (f) 1 J-5 (G=CH2CH2, Q=Ph) 6 (f) m J-5 (G=CH2CH2, Q=4-F-Ph) 6 (f) n J-5 (GzCH2CH2, Q=4-Cl-Ph)

7(g) a J-6 (G=CH2, Q=Me, R8=H) 7(g) b J-6 (G=CH2, Q=nPr, R8=H) W092/~76 ~3~i PCT/US91/07091 ~ 24 T~hle GroUP J

7(g) c J-6 (G=CH2, Q=iPr, R8=H) 7(g) d J-6 (GeCH2, QcCO2Me, R8~H) 7(g) e J-6 (G=CH2, Q=Ph, R8=H) 7(g) f J-6 (G=CH2, Q=4-F-Ph, R8~H) 7(g) g J-6 (G=CH2, Q=4-Cl-Ph, R8CH) 7(g) h J-6 (G=CH2CH2, Q=Me, R8eH) 7(g) i J-6 (G=CH2CH2, Q=nPr, R3eH) 7(g) j J-6 (G=CH2CH2, QciPr, R8eH) 7(g) k J-6 (G=CH2CH2, Q=CO2Me, R8=H) 7(g) 1 J-6 (G=CH2CH2, Q=Ph, R3=H) 7(g) m J-6 (G=CH2CH2, Q=4-F-Ph, R8=H) 7(g) n J-6 (G=CH2CH2, Q=4-Cl-Ph, R8'H)

8(h) a J-1 (A=CH2, Q=Me, R5=Me) 8(h) b J-1 (A=CH2, Q=nPr, R5=Me) 8(h) c J-1 (A=CH2, Q=iPr, R5=Me) g(i) a J-1 (A=CH2, Q=CO2Me, R5--Me) g(i) b J-1 (A=CH2, Q=Ph, R5eMe) g(i) c J-1 (A-CH2, Q=4-F-Ph, R5=Me) g(i) d J-1 (A=CH2, Q=4-Cl-Ph, R5=Me) g(i) e J-1 (A=CH2, Q=4-CF3-Ph, R5=Me) g(i) f J-l (A=CH2, Q=4-OCF2H-Ph, R5=Me) g(i) g J-1 (A=CH2, Q=4-OCF3-Ph, R5=Me) g(i) h J-1 (A=CH2, Q=4-Me-Ph, R5=Me) g~i) i J-1 (A=cPr, Q=Me, R5=Me) g(i) j J-1 (A=cPr, Q=nPr, R5=Me) g(i) k J-1 (A=cPr, Q=iPr, R5=Me) g(i) 1 J-1 (A=cPr, Q=CO2Me, R5=Me) g(i) m J-1 (A=cPr, Q=Ph, R5=Me) g(i) n J-1 (A=cPr, Q=9-F-Ph, R5=Me) g(i) o J-1 (A=cPr, Q=4-Cl-Ph, R5=Me) g(i) p J-1 (A=cPr, Q=4-CF3-Ph, R5=Me) W092/0~76 2 0 ~ 3 3 5 IPCT/US91/0709l T~hle Group J

g(i) q J-l (A=cPr, Q=4-OCF2H-Ph, R5=Me) g(i) r J-l (A=cPr, Q=4-OCF3-Ph, R5~Me) g(i) s J-1 (A=cPr, Q=9-Me-Ph, R5=Me) 10(j) a J-1 (A=CH2, Q=Me, R5=CO2Me) 10(j) b J-l (A=CH2, Q=nPr, R5=CO2Me) 10(j) c J-1 (A=CH2, Q=iPr, R5=CO2Me) 11(k) a J-1 (A=CH2, Q=CO2Me, R5=CO2Me) 11(k) b J-1 (A=CH2, Q=Ph, R5=CO2Me) 11(k) c J-l (A-CH2, Q=4-F-Ph, R5=CO2Me) l1(k) d J-l (A=CH2, Q=4-Cl-Ph, R5=CO2Me) l1(k) e J-l (A=CH2, Q=4-CF3-Ph, R5=CO2Me) 11(k) f J-1 (A=CH2, Q=4-OCF2H-Ph, R5=CO2Me) 11(k) g J-1 (A=CH2, Q=4-OCF3-Ph, R5=CO2Me) l1(k) h J-1 (A=CH2, Q=4-Me-Ph, R5=CO2Me) 11(k) i J-1 (A=cPr, Q=Me, R5=CO2Me) 11(k) j J-1 (A=cPr, Q=nPr, R5=CO2Me) 11(k) k J-1 (A=cPr, Q=iPr, R5=CO2Me) l1(k) l J-l (A=cPr, Q=CO2Me, R5=CO2Me) ll(k) m J-1 (A=cPr, Q=Ph, R5=CO2Me) 11(k) n J-1 (A=cPr, Q=4-F-Ph, R5=CO2Me) 11(k) O J-1 (A=cPr, Q=4-Cl-Ph, R5=CO2Me) 11(k) p J-1 (A=cPr, Q=4-CF3-Ph, R5=CO2Me) 11(k) q J-1 (A=cPr, Q=4-OCF2H-Ph, R5=CO2Me) l1(k) r J-1 (A=cPr, Q=4-OCF3-Ph, R5=CO2Me) 11(k) s J-1 (A=cPr, Q=4-Me-Ph, R5=CO2Me) 12(l) a J-l (A=CH2, Q-CO2Me, R5=H, R6=Me) 12(l) b J-1 (A=CH2, Q=Ph, R5=H, R6=Me) 12(l) c J-l (A=CH2, Q=4-F-Ph, R5=H, R6=Me) 12(l) d J-1 (A=CH2, Q=4-Cl-Ph, R5=H, R6=Me) 12(l) e J-1 (A=CH2, Q=4-CF3-Ph, R5=H, R6=Me) 12(l) f J-1 (A=CH2, Q=4-OCF2H-Ph, R5=H, R6=Me) W09Z/~76 ~ PCT/US9l/07~1 T~hle GroUP J

12(l) g J-1 (A=CH2, Q=4-OCF3-Ph, R5=H, R6=Me) 12(l) h J-1 (A=CH2, Q=4-Me-Ph, R5=H, R6=Me) 12(l) i J-1 (A=cPr, Q=Me, R5=H, R6=Et) 12(l) j J-1 (A=cPr, Q-nPr, R5CH, R6=Et) 12(1) k J-1 (A=cPr, Q=iPr, R5eH, R6=Et) 12(l) l J-1 (A=cPr, Q=CO2Me, R5=H, R6=Et) 12(l) m J-1 (A=cPr, Q-Ph, R5=H, R6=Et) 12(l) n J-l (A=cPr, Q=4-F-Ph, R5=H, R6=Et) 12(l) O J-1 (A=cPr, Q=4-Cl-Ph, R5=H, R6=Me) 12(l) p J-1 (A=cPr, Q=4-CF3-Ph, R5=H, R6=Et) 12(l) q J-1 (A=cPr, Q=4-OCF2H-Ph, R5=H, R6=Et) 12(l) r J-1 (A=cPr, Q=4-OCF3-Ph, R5=H, R6=Et) 12(l) s J-1 (A=cPr, Q=4-Me-Ph, R5=H, R6=Et) (a) Compounds of Table 1 wherein R1, R2 and R3 are as set out therein can be prepared having the recited values of groups a through c.
(b) Compounds of Table 2 wherein R1, R2 and R3 are as set out therein can be prepared having the recited values of groups a through s.
(c) Compounds of Table 3 wherein Rl, R2 and R7 are as set out therein can be prepared having the recited values of groups a through n.
(d) Compounds of Table 4 wherein R1, R2 and R8 are as set out therein can be prepared having the recited values of groups a through n.
(e) Compounds of Table 5 wherein R1, R2 and R7 are as set out therein can be prepared having the recited values of groups a through n.

_ 27 20g33S1 (f) Compounds of Table 6 wherein Rl, R3 and R7 are as set out therein can be prepared having the recited values of groups a through n.
(g) Compounds of Table 7 wherein R1, R3 and R7 are as set out therein can be prepared having the recited values of groups a through n.
(h) Compounds of Table 8 wherein R1, R2 and R3 are as set out therein can be prepared having the recited values of groups a through c.
(i) Compounds of Table 9 wherein R1, R2 and R3 are as set out therein can be prepared having the recited values of groups a through s.
(j) Compounds of Table 10 wherein R1, R2 and R3 are as set out therein can be prepared having the recited values of groups a through c.
(k) Compounds of Table 11 wherein R1, R2 and R3 are as set out therein can be prepared having the recited values of groups a through s.
(1) Compounds of Table 12 wherein R1, R2 and R3 are as set out therein can be prepared having the recited values of groups a through s.

W O 92/06076 ~ PC~r/US91/07091 ~9 28 TART.F. 1 Bl B2 B3 Bl B2 B3 Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
oSo2cF3 Br H OSO2CF3 OCF2H H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Br F H Br OCH3 H

oSo2cF3 F H OSO2CF3 OCH3 H

W O 92/06076 PC~r/US91/07091 TART.F. ~

Bl B2 B3 gl B2 B3 Cl Cl H Cl OCH2CF3 H
Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
OSO2CF3 Br H OSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

oSo2cF3 F H oSo2cF3 OCH3 H

TP~T.F, 3 Bl B2 B7 Bl B2 B7 Cl Cl H Cl OCH2CF3 H
Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
oSo2cF3 Br H OSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

oSo2cF3 F H OSO2CF3 OCH3 H

W O 92/06076 PC~r/US91/07091 _~ 31 ~D~33~

Bl B2 B7 Bl B2 B7 Cl Cl Me Cl OCH2CF3 Me Br Cl Me Br OCH2CF3 Me CF3 Cl Me CF3 OCH2CF3 Me OCF3 Cl Me OCF3 OCH2CF3 Me OCF2H Cl Me OCF2H OCH2CF3 Me oSo2cF3 Cl Me OSO2CF3 OCH2CF3 Me Cl Br Me Cl OCF2H Me Br Br Me Br OCF2H Me CF3 Br Me CF3 OCF2H Me OCF3 Br Me OCF3 OCF2H Me OCF2H Br Me OCF2H OCF2H Me OSO2CF3 Br Me oSO2CF3 OCF2H Me Cl CF3 Me Cl CN Me Br CF3 Me Br CN Me CF3 CF3 Me CF3 CN Me OCF3 CF3 Me OCF3 CN Me OCF2H CF3 Me OCF2H CN Me oSo2cF3 CF3 Me OSO2CF3 CN Me Cl F Me Cl OCH3 Me Br F Me Br OCH3 Me CF3 F Me CF3 OCH3 Me OCF3 F Me OCF3 OCH3 Me OCF2H F Me OCF2H OCH3 Me OSO2CF3 F Me OSO2CF3 OCH3 Me W092/06076 ~ PCT/US91/07091 TART.F. 4 Bl B2 B8 Bl B2 B8 Cl Cl H Cl OCH2CF3 H
Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
oSo2cF3 Br H OSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

oSo2cF3 F H OSO2CF3 OCH3 H

~0933~1 TART.F. 5 Bl B2 B7 Bl B2 B7 Cl Cl H Cl OCH2CF3 H
Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
OSO2CF3 Br H OSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

oSo2cF3 F H OSO2CF3 OCH3 H

~' Bl B2 B7 Bl B2 B7 Cl Cl Me Cl OCH2CF3 Me Br Cl Me Br OCH2CF3 Me CF3 Cl Me CF3 OCH2CF3 Me OCF3 Cl Me OCF3 OCH2CF3 Me OCF2H Cl Me OCF2H OCH2CF3 Me OSO2CF3 Cl Me OSO2CF3 OCH2CF3 Me Cl Br Me Cl OCF2H Me Br Br Me Br OCF2H Me CF3 Br Me CF3 OCF2H Me OCF3 Br Me OCF3 OCF2H Me OCF2H Br Me OCF2H OCF2H Me OSO2CF3 Br Me oSO2CF3 OCF2H Me Cl CF3 Me Cl CN Me Br CF3 Me Br CN Me CF3 CF3 Me CF3 CN Me OCF3 CF3 Me OCF3 CN Me OCF2H CF3 Me OCF2H CN Me OSO2CF3 CF3 Me OSO2CF3 CN Me Cl F Me Cl OCH3 Me Br F Me Br OCH3 Me CF3 F Me CF3 OCH3 Me OCF3 F Me OCF3 OCH3 Me OCF2H F Me OCF2H OCH3 Me OSO2CF3 F Me OSO2CF3 OCH3 Me W O 92/06076 PC~r/US91/07091 35 ~ 3 ~ 1 T~RT.F~ 6 Bl B3 B7 Rl B3 B7 Cl Cl H Cl OCH2CF3 H
Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
CSO2CF3 Br H OSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

oSo2cF3 F H oSo2cF3 OCH3 H

W092/06076 ~ PCT/US91/07091 ' ~ 36 Bl B3 g7 Bl B3 g7 Cl Cl Me Cl OCH2CF3 Me Br Cl Me Br OCH2CF3 Me CF3 Cl Me CF3 OCH2CF3 Me OCF3 Cl Me OCF3 OCH2CF3 Me OCF2H Cl Me OCF2H OCH2CF3 Me OSO2CF3 Cl Me OSO2CF3 OCH2CF3 Me Cl Br Me Cl OCF2H Me Br Br Me Br OCF2H Me CF3 Br Me CF3 OCF2H Me OCF3 Br Me OCF3 OCF2H Me OCF2H Br Me OCF2H OCF2H Me OSO2CF3 Br Me oSO2CF3 OCF2H Me Cl CF3 Me Cl CN Me Br CF3 Me Br CN Me CF3 CF3 Me CF3 CN Me OCF3 CF3 Me OCF3 CN Me OCF2H CF3 Me OCF2H CN Me OSO2CF3 CF3 Me OSO2CF3 CN Me Cl F Me Cl OCH3 Me Br F Me Br OCH3 Me CF3 F Me CF3 OCH3 Me OCF3 F Me OCF3 OCH3 Me OCF2H F Me OCF2H OCH3 Me OSO2CF3 F Me OSO2CF3 OCH3 Me W O 92/06076 PC~r/US91/0709 37 2~ 35 TART.F~ 7 Bl B3 B7 Bl B3 B7 Cl Cl H Cl OCH2CF3 H
Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
OSO2CF3 Br H OSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

W O 92/06076 PC~r/US91/07091 ~ 38 Bl B3 B7 Bl B3 B7 Cl Cl Me Cl OCH2CF3 Me Br Cl Me Br OCH2CF3 Me CF3 Cl Me CF3 OCH2CF3 Me OCF3 Cl Me OCF3 OCH2CF3 Me OCF2H Cl Me OCF2H OCH2CF3 Me OSO2CF3 Cl Me OSO2CF3 OCH2CF3 Me Cl Br Me Cl OCF2H Me Br Br Me Br OCF2H Me CF3 Br Me CF3 OCF2H Me OCF3 Br Me OCF3 OCF2H Me OCF2H Br Me OCF2H OCF2H Me oSo2cF3 Br Me oSo2cF3 OCF2H Me Cl CF3 Me Cl CN Me Br CF3 Me Br CN Me CF3 CF3 Me CF3 CN Me OCF3 CF3 Me OCF3 CN Me OCF2H CF3 Me OCF2H CN Me OSO2CF3 CF3 Me OSO2CF3 CN Me Cl F Me Cl OCH3 Me Br F Me Br OCH3 Me CF3 F Me CF3 OCH3 Me OCF3 F Me OCF3 OCH3 Me OCF2H F Me OCF2H OCH3 Me oSo2cF3 F Me oSo2cF3 OCH3 Me 20933sl TART.F: 8 Bl B2 B3 Bl B2 B3 Br Cl H Br OCH2CF3 H
CF3 Cl H CF3OCH2CF3 H
OCF3 Cl H OCF3OCH2CF3 H
OCF2H Cl H OCF2HOCH2CF3 H
oSo2cF3 Cl H OS2CF3 OCH2CF3 H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
OSO2CF3 Br H OSO2CF3 OCF2H H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Br F H Br OCH3 H

oSo2cF3 F H oSo2cF3 OCH3 H

TART,F~ 9 Bl B2 B3 Bl B2 B3 Cl Cl H Cl OCH2CF3 H
Br Cl . H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br, H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
oso2CF3 Br H OSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

oSo2cF3 F H OSO2CF3 OCH3 H

W O 92/06076 PC~r/US91/07091 T~F~T.F. 1 0 Bl B2 B3 Bl ~2 B3 Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
OSO2CF3 Br H OSO2CF3 OCF2H H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Br F H Br OCH3 H

CSO2CF3 F H OSo2cF3 OCH3 H

W O 92/06076 ~C~r/US91/07091 ~ ~ 42 Q

TART.F. 1 1 Bl B2 B3 Bl B2 B3 Cl Cl H Cl OCH2CF3 H
Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Cl Br H Cl OCF2H H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
OSO2CF3 Br H oSO2CF3 OCF2H H
Cl CF3 H Cl CN H
Br CF3 H Br CN H

oSo2cF3 CF3 H OSO2CF3 CN H
Cl F H Cl OCH3 H
Br F H Br OCH3 H

oSo2cF3 F H OSO2CF3 OCH3 H

W O 92/06076 PC~r/US91/07091 _ 43 2 0 9 3 3 5 TART.F. 1 2 Bl B2 B3 Bl B2 B3 Br Cl H Br OCH2CF3 H
CF3 Cl H CF3 OCH2CF3 H
OCF3 Cl H OCF3 OCH2CF3 H
OCF2H Cl H OCF2H OCH2CF3 H
oSo2cF3 Cl H OSO2CF3 OCH2CF3 H
Br Br H Br OCF2H H
CF3 Br H CF3 OCF2H H
OCF3 Br H OCF3 OCF2H H
OCF2H Br H OCF2H OCF2H H
oSo2cF3 Br H OSO2CF3 OCF2H H
Br CF3 H Br CN H

Br F H Br OCH3 H

OSO2CF3 F H oSo2cF3 OCH3 H

W092/~076 ~ PCT/US91/07~1

9~
~ 44 For~ul~tion ~n~ Use The compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the li~e. Many of these can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare.
High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain from less than about 1~ to 99% ~y weight of active ingredient(s) and at least one of a) about 0.1%
to 20% surfactantts) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain effective amounts of these ingredients in the following approximate proportions:

Percent hy Weipht Active Tn~re~ient Diluent(s) Surf~ct~nt(s) Wettable Powders 25-90 0-74 1-10 Oil Suspensions, 5-50 40-95 0-15 Emulsions, Solutions, (including Emulsifiable Concentrates) Dusts 1-25 70-99 0-5 Granules, Baits 0.01-955-99 0-15 and Pellets High Strength 90-99 0-10 0-2 Compositions W092/~076 PCT/US91/07091 45 20933S1 j Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Eooks, Caldwell, New Jersey.
The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950.
Solubility under O.l~ is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at O~C. "McCutcheon's Detergents and Emulsifiers Annual", Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ.
Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, U.S. 3,060,084). Granules and pellets can be made by spraying the active material upon W O 92/06076 ~ ~ PC~r/US91/07091 q"Q
preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Ch~m;c~l Fng;neer;n~, December 4, 1967, pages 147 and following, and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following.

Fx~ple A
.mulSif; ~hl e Concentr~te [1-(3-chlorophenyl)-2-phenylethylidene]-N-[4-(trifluoromethyl)phenyl]hydrazinecarboY.amide 20%
blend of oil soluble sulfonates and polyoxyethylene ethers 10%
isophorone 70%
The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.

F.X ~TrU~ 1 e R
Wett~hle Pow~er [1-(3-chlorophenyl)-2-phenylethylidene]-N-[4-(trifluoromethyl)phenyl]hydrazinecarboxamide 30~
sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2~
synthetic amorphous silica 3%
kaolinite 63%
The active ingredient is mixed with the inert materials in a blender. After gr.inding in a hammermill, the material is re-blended and sifted through a 50 mesh 3S screen.

W092/0~76 PCT/US91/07091 _ 47 20933.

~x~ple C
Dust Wettable powder of Example B 10%
pyrophyllite (powder) 90%
The wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust.

F.~;~mpl e D
Gr~nule [1-(3-chlorophenyl)-2-phenylethylidene]-N-[4-(trifluoromethyl)phenyl]hydrazinecarboxamide 10%attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90%
The active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender.
The acetone is then driven off by heating. The granules are then allowed to cool and are packaged.

Fy~ple F.
Gr~nule Wettable powder of Example B 15%
gypsum 69%
potassium sulfate 16%
The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient.

W O 92/06076 ~ PC~r/US91/0709 ~ 48 q~ F.x;~ pl e F
Solut;on [1-(3-chlorophenyl)-2-phenylethylidene]-N-~4-(trifluoromethyl)phenyl]hydrazinecarboxamide 25%
N-methylpyrrolidone 75%
The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.

F.~ rl e G
Aeueous ~uspens; on [1-(3-chlorophenyl)-2-phenylethylidene]-N-[4-(trifluoromethyl)phenyl]hydrazinecarboxamide 40%
polyacrylic acid thickener 0.3%
dodecyclophenol polyethylene glycol ether 0.5%
disodium phosphate 1.0%
monosodium phosphate 0.5%
polyvinyl alcohol 1.0%
water 56.7%
The ingredients are blended and ground together in a sand mill to produce particles substantially all under 5 microns in size.

F,x?~ p le Y
Oil Suspension [1-(3-chlorophenyl)-2-phenylethylidene]-N-[4-(trifluoromethyl)phenyl]hydrazinecarboxamide 35.0%
blend of polyalcohol carbo~ylic 6.0%
esters and oil soluble petroleum sulfonates xylene range sol~ent 59.0%
The ingredients are combined and ground together in a sand mill to produce particles substantially all below W O 92/06076 PC~r/US91/07091 49 2 ~ 9 3 3 5 I~

5 microns. The product can be used directly, extended with oils, or emulsified in water.

~le ~it Gr~nl~les [1-(3-chlorophenyl)-2-phenylethylidene]-N-[4-(trifluoromethyl)phenyl]hydrazinecarboxamide 3.0%
blend of polyethoxylated nonyl- 9.0%
phenols and sodium dodecylbenzene sulfonates ground up corn cobs 88.0%
The active ingredient and surfactant blend are dissolved in a suitable solvent such as acetone and sprayed onto the ground corn cobs. The granules are then dried and packaged.
Compounds of Formula I can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of effective agricultural protection. EY.amples of other agricultural protectants with which compounds of this invention can be formulated are:

Insectic;~es:
3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofuran) 0-[2,4,5-trichloro-a-(chloromethyl)benzyl~phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) 092/06076 ~ ~ PCT/US91/07~1 c~
~9~ 50 phosphorothioic acid, O,O-dimethyl, O-~-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with a-naphthol (carbaryl~
methyl O-(methylcarbamoyl)thiolacetohydroxamate (methomyl) N'-(4-chloro-~-tolyl)-N,N-dimethylformamidine (chlordimeform) O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphos-phorothioate (diazinon) octachlorocamphene (toxaphene) 1~ O-ethyl-O-p-nitrophenyl phenylphosphonothioate (EPN) (S)-a-cyano-m-phenoxybenzyl(lR,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (deltamethrin) Methyl-N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-l-thioox amimidate (oxamyl) cyano(3-phenoxyphenyl)-methyl-4-chloro-a-(1-methyl-ethyl)benzeneacetate (fenvalerate) (3-phenoxyphenyl)methyl(+)-~i~,tr~ns-3-(2,2-dichloro ethenyl)-2,2-dimethylcyclopropanecarboxylate (permethrin) a-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate (cypermethrin) O-ethyl-S-(~-chlorophenyl)ethylphosphonodithioate (profenofos) phosphorothiolothionic acid, O-ethyl-0-[4-(methylthio)-phenyl]-S-n-propyl ester (sulprofos) Additional insecticides are listed hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotphos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, W092/0~76 PCT/US91/07~1 . 51 20933~1-terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone.

Fun~ici~es:
methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarbamate (maneb) 1,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl) 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-lH-1,2,4-triazole (propiconazole) 2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil) l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-1,2,4-triazol-1-yl)-2-butanone (triadimefon) N-(trichloromethylthio)tetrahydrophthalimide (captan) N-(trichloromethylthio)phthalimide (folpet) l-[[[bis(4-fluorophenyl)][methyl~silyl~methyl]-lH-1,2,4-triazole Nematoci~es:
S-methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)-thioformimidate S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)thio-formimidate N-isopropylphosphoramidic acid O-ethyl 0'-[4-(methyl-thio)-m-tolyl]diester (fenamiphos) W092/~076 ~ ~ PCT/US91/07~1 ~Q~ 52 R~cter;ci~es:
tribasic copper sulfate streptomycin sulfate Ac~r;c;~es:
senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl) 6-methyl-1,3-cithiolo[4,5-~]quinoxalin-2-one (oxythioquinox) ethyl 4,4'-dichlorobenzilate (chlorobenzilate) 1,1-bis(~-chlorophenyl)-2,2,2-trichloroethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-thiazolidine-3-carboxamide (hexythiazox) amitraz propargite fenbutatin-oxide Ri olo~;c~l Bacillus thuringiensis Avermectin B

Uti~ity The compounds of this invention exhibit activity against a wide spectrum of foliar and soil inhabiting arthropods which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will recognize that not all compounds are equally effective against all agronomic and nonagronomic pests but the compounds of this invention display W092/~076 2093~S PCT/US91/07091 _ 53 activity against economically important agronomic, forestry, greenhouse, ornamental food and fiber product, stored product, domestic structure, and nursery pests, such as:

larvae of the order Tepi~opter~ including fall and beet armyworm and other .~po~opter~ ~p., tobacco budworm, corn earworm and other ~el;oth;s ~p., European corn borer, navel orangeworm, stalk/stem borers and other pyralids, cabbage and soybean loopers and other loopers, codling moth, grape berry moth and other tortricids, black cutworm, spotted cutworm, other cutworms and other noctuids, diamondback moth, green cloverworm, velvetbean caterpillar, green cloverworm, pink bollworm, gypsy moth, and spruce budworm;

foliar feeding larvae and adults of the order Coleoptera including Colorado potato beetle, 2~ MeY.ican bean beetle, flea beetle, Japanese beetles, and other leaf beetles, boll weevil, rice water weevil, granary weevil, rice weevil and other weevil pests, and soil inhabiting insects such as Western corn rootworm and other Di~hrotic~ ., Japanese beetle, European chafer and other coleopteran grubs, and wireworms;

adults and larvae of the orders ~emipter~ and Ho~o~ter~ including tarnished plant bug and other plant bugs (~iri~e), aster leafhopper W092/0~76 PCT/US91/07091 ~ 54 S ~ and other leafhoppers (c;c~ell;~e), rice planthopper, brown planthopper, and other planthoppers ~f~ oroi~e~), psylids, whiteflies (~leuroA;~e), aphids (~ph;~e), scales (cocc;~e and ~;~sp;~ e), lace bugs (t;ngi~e), stink bugs (pent~to~ e), cinch bugs and other seed bugs (ly~el~e), cicadas (c;c~ e), spittlebugs (cercop;~s), squash bugs (core;~e), red bugs and cotton stainers (pyrrhocori~e);
adults and larvae of the order ~c~ri (mites) including European red mite, two spotted spider mite, rust mites, McDaniel mite, and foliar feeding mites;
adults and immatures of the order Orthoptera including grasshoppers;

adults and immatures of the order D;ptera including leafminers, midges, fruit flies (tephritidae), and soil maggots;

adults and immatures of the order Thys~no~tera including onion thrips and other foliar feeding thrips.

The compounds are also active against economically important livestock, household, public and animal health pests such as:
insect pests of the order ~ymenopter~ including carpenter ants, bees, hornets, and wasps;

W092/0~76 PCT/US91/07091 insect pests of the order D;pter~ including house flies, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other Rr~c~ycer~, mosquitoes, black flies, biting midges, sand flies, sciarids, and other N~m~tocer~;

insect pests of the order Orthopter~ including cockroaches and crickets;
insect pests of the order Isopter~ including the Eastern subterranean termite and other termites;
insect pests of the order M~lloph~ and Anoplllr~ including the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals;

insect pests of the order ~;pho~opter~ including the cat flea, dog flea and other fleas.
The speclfic species for which control is exemplified are: fall armyworm, Spo~opter~ fruigiper~a;
tobacco budworm, ~eliothis virescens; boll weevil, Anthono~us ~r~n~is; aster leafhopper, M~crosteles f~sc;frons; black bean aphid, (A~his F~h~e); southern corn rootworm, Di~hrotic~ un~eci~pl~nct~t~. The pest control protection afforded by the compounds of the present invention is not limited, however, to these species. The compounds of this invention may also be utilized as rodenticides.

W092/~076 ~ PCT/US91/07091 ~9 S6 ~p~lic~t;on Arthropod pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the Formula I compounds, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these arthropod pest species, many different methods of application are employed. A
preferred method of application is by spraying with equipment that distributes the compound in the environment of the pests, on the foliage, animal, person, or premise, in the soil or animal, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these toxicant compounds can be applied to or incorporated into the soil. Other methods of application can also be employed including direct and residual sprays, aerial sprays, baits, eartags, boluses, foggers, aerosols, and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compounds.
The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, and synergists such as piperonyl butoxide often enhance the efficacy of the compounds of Formula I.

W092/0~76 PCT/US91/07091 _ 57 20933~1 The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, etc. In general, application rates of 0.01 to 2 kg of active ingredient per hectare are sufficient to provide large-scale effective control of pests in agronomic ecosystems under normal circumstances, but as little as 0.001 kg/hectare or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as about 0.1 mg/square meter or as much as 150 mg/square meter may be required.
The following tests demonstrate the control efficacy of compounds of Formula I on specific pests; see Index Table A for compound descriptions. Compounds not included in the test result summaries were either not screened or produced less than the recited threshold 2~ mortalities.

C~ TNDF.X T~RT.F. A

Q-A ~ N- NH ~ ~ R

~R2 Co~ol-n~ gl B2 ~ Q ~r (C) 1 CF3 Cl CH2 Ph 225-229 2 OCF3 Cl CH2 Ph 201-208 3 CF3 CF3 CH2 Ph 201-206 4 OCF3 CF3 CH2 Ph 190-193 OCF3 CF3 CH2 4-F-Ph 164-171 6 CF3 CF3 CH2 n-Pr 160-162 7 OCF3 CF3 CH2 n-Pr 156-157 8 Cl CF3 CH2 n-Pr white solid 9 Br CF3 CH2 n-Pr white solid CF3 Cl CH2 Me 210-218 11 OCF3 Cl CH2 Me 200-209 12 Cl Cl CH2 Me 220-237 13 Br Cl CH2 Me white solid 14 CF3 CF3 CH2 Me 185-195 OCF3 CF3 CH2 Me 178-185 16 CF3 F CH2 4-F-Ph 200-212 17 OCF3 F GH2 4-F-Ph 180-189 18 CF3 CF3 CH2 4-F-Ph 185-193 19 CF3 Cl CH2 4-F-Ph 204-208 OCF3 Cl CH2 4-F-Ph 168-177 21 CF3 CF3 CH2 4-CF3-Ph 145-169 22 OCF3 CF3 CH2 4-CF3-Ph 160-170 W092/06076 PCT/US9l/07091 _ 59 2093351 Co~pol~nd Bl B2 ~ Q ~p (C) 23 CF3 CF3 CH2 i-Pr 185-190 24 OCF3 CF3 CH2 i-Pr 144-150 CF3 Cl CH2 i-Pr 172-184 26 OCF3 Cl CH2 i-Pr 158-163 27 CF3 CF3 CH(Me) Me 145-151 28 OCF3 CF3 CH(Me) Me 105-120 29 CF3 CF3 C(Me)2 Me 105-118 OCF3 CF3 C(Me)2 Me 105-115 Q - A ~ N-N-CNH ~\ ~ ~ R1 [~ R2 Phys.
Compound B1 B2 R5 ~ Q Prop.

31 CF3 CF3 co2Me CH2 i-Pr solid N~ CNH ~ Rl Co~pol~nd Bl B2 B4 ~ (C) _ 61 2093351 N

N ~ O

Compol~nd Bl B2 B4 ~P (C) 36 OCF3 Cl F 157-159 37 CF3 Cl F 192-194 38 OCF3 Cl H 186-188 39 CF3 Cl H 210-212 W 092/06076 ~ ~ PC~r/US91/07091 ~ ~ 62 Tnsect;c;~e Test Protocols Co~poun~ ~p~l;c~t;on Experimental compounds are formulated in a 75:25 acetone:water solution, unless otherwise indicated. All compounds are initially tested at 1000 ppm. The formulated compound is applied with a single, flat fan 8001E nozzle positioned 7.5 inches (19 cm) above the test units which are situated on a conveyor belt. Spray pressure is maintained at 30 psi (207 kPa), and the conveyor speed is adjusted so that 6 ml of test solution is sprayed per 0.1 square meter of conveyor at a rate of 0.5 pounds (0. 2 kg) of active ingredient per acre (0.55 kg/ha). Three untreated (blanks) and three solvent-treated test units are run for each insect species tested.
F.~MPT.F. J
Fall Armyworm (FAW) ~po~opter~ frug;per~
Acute Toxicity: Two lima bean leaf discs, each with a surface area of 8.1 cm2 were sprayed top side up along with 7-12 3rd instar, unstarved fall armyworm larvae.
The treated lima bean leaves were placed top side up in a 15 mm x 100 mm petri dish that had been lined with filter paper moistened with 1.5 ml of water. After the leaf discs had dried, 5 sprayed larvae were introduced into the petri dish. Larval mortality was assessed at 48 hours post-treatment. Of the compounds tested, the following produced 80% mortality or greater: Compounds 1, 2, 3, 5, 6, 16, 17, 18, 20, 21J 22, 23, 24, 25, 26, 28, 31, 32, 33, 36, 37, 40 and 41~.
Antifeedant Test: At the 48 hour acute toxicity assessment, the amount of each leaf disc eaten was determined and expressed as percent reduction in feeding relative to controls. Of the compounds tested, the W092/06076 2 o 9 3 PCT/US9l/07091 _ 63 following induced feeding reduction of 75% or greater:
Compound 1.
F~ X P\~IP T .F. K
Tobacco Budworm (TBW) ~elio~h;s v'rescens (he~;coverp~) Five 3rd instar larvae were placed in an 8 oz (230 ml) cup containing artificial diet and sprayed with the test solution. Larval mortality was assessed at 48 hours post-treatment. Of the compounds tested, the following produced 80~ mortality or greater: Compounds 2, 3, 4, 5, 15 6, 7, 18, 20, 21, 22, 23, 24, 26, 27, 28, 31, 32, 33, 36, 37, 38, 40 and 41*.
F~ X ~IP T .F. T .
Southern Corn Rootworm (SCRW) Di~hrot;c~ lln~ec;~punct~t~ how~r~l An 8 oz (230 ml) dish containing a germinated corn kernel was sprayed with the test solution. After the spray had dried, five unsprayed, 3rd instar corn rootworm larvae were placed in the dish along with a moistened cotton wick. Larval mortality was assessed at 48 hours post-treatment. Of the compounds tested, the following produced 80% mortality or greater: Compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17, 18, 19, 20, 23, 24, 25, 26, 27, 28, 31, 32, 35, 36, 37, 38, 39, 40 and 41*.
F~X~IPT.Fl M
Boll Weevil tBw) Anthonomus ~r~n~;s ~r~n~;s A filter paper-lined 9 oz (260 ml) plastic tumbler containing 5 adult boll weevils was sprayed with the test solution. The treated cups were capped with a paper lid with an opening cut into it, and placed in a ventilated room to dry for several hours. Mortality was assessed at 48 hours post-treatment. Of the compounds tested, the W O 92/06076 . ~ PC~r/US91/07091 ~ 64 following produced 80% mortality or greater: Compounds 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 26, 27, 28, 31, 33, 35, 36, 37, 38, 39, 40 and 41*.
F.XA~IPT.F. N
Aster Leafhopper (AL~) M~crosteles ~u~r;~ine~tus Six day old oat seedlings planted in a 12oz(350 ml) cup with a layer of white sand covering the soil were sprayed with the test solution. The treated test unit was allowed to dry and then capped. Leafhoppers were aspirated into the test unit through an opening in the lid. At least 15 adult leafhoppers were introduced into the test unit and the opening was sealed with a piece of cotton gauze. Mortality was assessed at 48 hours post-treatment. Of the compounds tested, the following 20 produced 80% mortality or greater: Compounds 1, 5, 23, 24, 25, 26, 28, 31, 36, 37 and 40.

*Compound tested at 250 ppm.

Claims (12)

1. A compound of the formula I

wherein J is selected from the group , , , , and wherein A is a single bond or selected from the group C1-C3 alkylene and C3-C6 cycloalkylene each of which is optionally substituted with 1 or 2 R9;
G is C1-C2 alkylene optionally substituted with 1 or 2 CH3;
Q is selected from the group H, R9, phenyl optionally substituted with (R4)p, thienyl optionally substituted with W, pyridinyl optionally substituted with W, C1-C6 alkyl optionally substituted with R9 and C3-C6 cycloalkyl optionally substituted with R9;
provided that when J is J-1 and A is methylene, then Q is other than H;
X is selected from the group O and S;
Z is selected from the group N and CH:
R1, R, R3 and R4 are independently selected from the group halogen, CN, SCN, R10, OR10, S(O)qR10, OSO2R10, C(O)R10, CO2R10, C(O)N(R10)R11, SO2N(R10)R11 and N(R10)R1?0; and when m, n or p is 2, (R1)2, (R3)2, (R4)2 or R and R3 when attached to adjacent atoms can be taken together as OCH2O, OCF2O, OCH2CH2O, OCH2C(CH3)2O or OCF2CF2O to form a cyclic bridge; provided that when R is Cl then R3 is other than Cl;

R5 and R6 are independently selected from the group H, C1-C6 alkyl, C2-C6 alkoxyalkyl, CHO, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 haloalkylcarbonyl, C1-C6 alkylthio, C1-C6 haloalkylthio, R12OC(O)N(R13)S-, R15(R14)NS- and benzyl optionally substituted with W;
R7 is selected from the group H, C1-C6 alkyl,C1-C6 haloalkyl and phenyl optionally substituted with W;
R8 is selected from the group H, C1-C3 alkyl, CO2R10 and C(O)N(R10)R11;
R9 is selected from the group halogen, NO2, CN, C1-C3 alkyl, C1-C3 haloalkyl, OH, OR10, S(O)qR10, N(H)R11, N(R10)R11 and CO2R10;
R10 is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C3-C4 alkynyl, C3-C4 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 cyanoalkyl, C3-C6 alkoxycarbonyl alkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 alkylcycloalkyl, C4-C7 haloalkylcycloalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benzyl substituent(s) are 1 to 3 substituents independently selected from W;
R11 is selected from the group H and C1-C4 alkyl;
R12 and R13 are independently selected from C1-C6 alkyl;
R14 and R15 are independently selected from C1-C4 alkyl; or R14 and R15 when attached to the same atom can be taken together as (CH2)5 or CH2CH2OCH2CH2;

W is selected from the group halogen, CN, NO2, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C3 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfonyl, and C1-C2 haloalkylsulfonyl;
m is 0 to 2;
n is 1 to 2;
p is 0 to 2; and q is 0 to 2.

2. A compound according to Claim 1 wherein:
A is selected from the group C1-C3 alkylene and C3-C6 cycloalkylene each of which is optionally substituted with 1 or 2 R9;
G is C1-C2 alkylene substituted with 1 or 2 CH3;
Q is selected from the group CO2R10, phenyl optionally substituted with (R4)p, C1-C6 alkyl optionally substituted with R9 and C3-C6 cycloalkyl optionally substituted with R9;
X is O;
R1, R2, R3 and R4 are independently selected from the group halogen, CN, R10, OR10, S(O)qR10 and OSO2R10;
R5 and R6 are independently selected from the group H, C1-C2 alkyl, C2-C3 alkylcarbonyl and C2-C3 alkoxycarbonyl;
R7 is selected from the group H and CH3;
R8 is H;
R9 is selected from the group halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, OH, S(O)qR10 and CO2R10;

R10 is selected from the group C1-C3 alkyl and C1-C3 haloalkyl;
R11 is selected from the group H or CH3;
W is selected from the group halogen, CN, NO2, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfonyl, and C1-C2 haloalkylsulfonyl;
m is 0 to 1;
n is 1 with R1 in the para-position;
p is 0 or 1; and q is 0 or 2.

3. A compound according to Claim 2 wherein J is J-1.

4. A compound according to Claim 2 wherein J is J-2.

5. A compound according to Claim 2 wherein J is J-3.

6. A compound according to Claim 2 wherein J is J-4.

7. A compound according to Claim 2 wherein J is J-5.

8. A compound according to Claim 2 wherein J is J-6.

9. A compound according to Claim 2 wherein A is C1-C2 alkylene optionally substituted with 1 or 2 methyl groups.

10. A compound according to Claim 3:
2-12-phenyl-1-[3-trifluoromethyl)phenyl]-ethylidene]-N-[4-(trifluoromethoxy)-phenyl]hydrazine carboxamide.

11. An arthropodicidal composition comprising a compound according to any one of Claims 1 to 10 and a carrier therefor.

12. A method for controlling arthropods comprising contacting them or their environment with an arthropodicidally effective amount of a compound according to any one of Claims 1 to 10.