PH26417A - Compositions for and method of controlling rice insects using N'-substituted-N,N'-diactylhydrazines - Google Patents

Description

So | acy 26417 v

COMPOSITIONS FOR AND METHOD OF CONTROLLING RICE

INSECTS USING N’-BUBSTITUTED-N,N’-DIACYLHYDRAZ INES

Background and Bummary of Invention ee mr ee et em et ert 0 i te ee fe on tm

The present invention recognizes that N’- substituted-N,N’'~diacylhydrazines have properties which make them particularly useful for controlling insects in rice crops. Additionally, compositions containing these compounds are also useful as insecticides in rice crops. More specifically, the invention relates to compositions : and a method for controlling insects in the locus of a rice field with an insecticidally-effective amount of a compound of the formula:r 0 0 fl ]

A—-C~NH~-N-C-A"’ Formula 1 wherein R is tert-butyl or necpentyly = A is 2- . pyridyl, phenyl or phenyl substituted with one or two substituents each independently selected from ; the group consisting of 2- or 4-halo, 2,3 or 2,6 dihalo, 4-{C4-Ca)alkyl, 2,3-d1 (C4-Co) alkyl, 2-(Cy-

Co) alkyl-3-hala, 2-halo-3-(Cq-Cg)alkyl, .2,3-di(Cy- !

Colalkoxy and 2- or 3- (Cy-Cp)alkoxyj ‘ar 1m 1- methylethenyl, phenyl or phenyl substituted with one or two substituents each independently selected from 2-, 3-, or 4-halo, 3,5 3,4~ or 2,4 dihalo, 3-

CT : 2 de Ie

= oa we on = i od (Cy-Cod alkyl, 3,5-di(C;-Cp)alkyl, 3 (Cy ~Cg) al kyl -5- halo and 2-halo-3-(Cy-C,) alkyl, provided A and a are not both (unsubstituted) phenyl) and agronomically-acceptable salts thereof.

S The term halo as it applies to this invention means chloro, fluoro, bromo and iodo atoms.

The preferred moiety for the R substituent is tert-butyl. Preferred moieties for the A substituent are phenyl and substituted phenyl wherein the substituents are 4-halo, 4-(Ci{-Calalkyl or 2,3-di(C{-Cplalkyl or 2,6-dihalo, preferably 2,46~di fluoro. Preferred moieties for the a’ substituent are subutituted phenyls wherein the . } substituents are 2-halo, 2,4-dihalo, 3-(Cy4~Ca)alkyl of 3,5-di (Cy-Cp) alkyl.

More preferred moieties for the A substituent are phenyls substituted with 4-methyl, 4-ethyl, 2,4-difluora or 2,3-dimethyl and more preferred moieties for the A’ substituent are phenyls - 20 sibati tuted with 2-chloro, 2,4-dichloro, - 2-chloro- a-f1uora, 3-methyl or 3,85-dimethyl. Le - : More preferred compounds of Formula’ for use in controlling insect pests of rice ares 1=(3,5-d1 nathyl benzoyl) ~2- (4-ethyl benzoyl) ~i-tert- butylhydrazine, 1-(3-methylbanzoyl )~2-(2;3-di= \

CL methylbenzoyl)-1-tert-butylhydrazine, 1-(3,9- di methylbenzoyl) —2- (4-methylbenzoyl)-1-tekt-butyl- ! hydrazine, {= (2-chl oro—4-£1uorobenzoyl ) ~2-benzoyl - ; i-tert-butylhydrazine and 1-(2,4-dichlorabenzoyl)- 3 . - loro ORIGINAL A

: ail} 26417 . I. 2-(2,6-di f1uorobanzayl) ~1-tert-butylhydrazine.

The compounds of Formula I exhibit weveral properties which make them particularly } advantageous for use in rice crops and for use in . 3 pasticidal compositions used in rice. For sxample, the compounds exhibit high toxicity against many important insects which {invade rice, "including those of the orders Lepidoptera and Homoptera.

Another advantage of the compounds of Formula

I is their low toxicity against mammals, birds, crustaceans and fish as well as beneficial insects : such as lady beetles, which feed on aphids and scale pests, spiders, flys, wasps and true bugs of i . the order Hemiptera. This makes these compounds 13 particularly suitable for use in rice since fish and crustaceans, e.g., shrimp, are often raised in rice paddies and geese and ducks are often used to control other insects in the vicinities of rice paddies. Moreover, rice paddy water usually flows — 20 or migrates into other water sources which are used i by mammals, birds, crustaceans and fish. i‘ - The diacylhydrazines of Formula I are readily . absorbed by the rice root system and’ exhibit systemic activity in the rice. This property makes 29 the compounds particularly useful in controlling : rice borers which are difficult to codtrol by : foliar dust or spray applications of insecticides.

Moreover, the systemic distribution of the compounds in the rice plants may result in the need a

2a} for fewer applications. Additionally, because the compounds cause little adverse effect on rice, the compounds are particularly useful in rice where phytotoxicity effects are consi dered highly 3 undesirable.

The compounds used in the present invention are useful against rice Lepidoptera belonging to the families: (1)Pyralidae, rice borers, for example, spotted stalk borer (Chilo | partellus (8winhoe) , rice stem borer (Chilo suppressalis(Wlk.)), white rice borer (Maliarpha separatella Rag.), rice case worm {(Nymphula depunctalis (Gn.)), rice leafroller (Cnaphalocrocis meadinalis(Buen.)) and yellow and white paddy stem borers (Tryporyza incertulas (Wlk.) and To innotata (Wlk.))y (2) Noctuidae, rice —— for example, Mythimna unipuncta (Haw.) M., separata (Wlk.) and HM. loreyi (Dup.), purple stem borer (Seasamla inferens (Wlk.)), beet armyworm (Spodoptera exigua (Hb.)) and paddy armyworm : (Spodoptera mauritia (Boisd.))y and (3) Hasperidae, . rice skippers, for example rice skippers (Telicota ! augias(L.)), Pelopidas mathias(F.)) rice leaf R scaler (Parnara guttata (Bremer Brey), and

Ampittia dioscorides. ’ :

The compounds used in the present invention are almo useful against rice Homoptera belonging to the families: (1) Cicadellidae, lwafhoppars, for example, green leafhoppers (Nephotettix cinctinceps '

- Da 14 26417 © {Uh1.) and Nephotettix impicticeps Ishiwara), green rice leafhopper (Nephotettix nigropictus (Stal.)) and zig-zag winged leafhopper (Inazuma dorsalis (Matsch.)); and (2) Delphacidae, planthoppers, for : 5 example, brown planthopper (Nilaparvata lugens (Stal.).

The compounds used in the present invention are especially effective against larvae of

Lepidoptera, particularly rice stem borer (Chilo suppressalis (Wik.)), rice leaf folder or rice leaf roller (Cnaphalocrocis medinalis (Buen), rice

RrMyWor ms (Spodoptera sp.)) and rice skipper (Telicota augias (L.)) and nymphs of Homptera, ‘ particularly green rice leafhopper (Nephotettix cincticeps (Uhl)). oo

When the compounds of Formula I have A as phenyl or a substituted phenyl, Ar as i- methylethenyl, phenyl or a substituted phany1 and R as tert-butyl or neopentyl, they can be prepared by - 20 Process Ax

Base rh

A-C (0) -C) + NHzNHR mmm A=-C (0) ~NH-NHR

Solvent

II 111 Iv

Base

A-C (0) ~NH-NHR + A’'-C(0)-C]l —~—===-> A-C(0)-~NH-NR-C(O)-A’

Sol vent oo

Vv Vv 1 - In process A, a compound of Formula II is reacted with an equivalent of a manosubstituted 23 hydrazine of Formula III or a corresponding acid : .

2G addition salt such as the hydrochloride salt or the like in the presence of a base in an inert ar substantially inert solvent or mixture of solvents to afford an intermediate product of Formula IV 3 which can be isolated or further reacted with a compound of Formula V in the presence of a base in an inert or substantially inert solvent or mixture of solvents to yleld the desired product of Formula

I. when A and A’ are the same, for example, both

A and A’ are 4-chlorophenyl, two equivalents of a compound of Formula II or V are reacted with an equivalent monosubstituted hydrazine of Formula III in the presence of a base in an {inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula I. The compounds of Formula 11 and/or Formula V are generally commercially available or can be prepared by known procedures. _ 20 Compounds of Formula 111 which are used in \ the above process are t-butylhydragine and . neopentylhydrazine. These are commercially available and can be prepared by known procedures. ’ For example, the Brignard reagent addition product of acetone azine in diethyl ether is hydrolyzed by the addition of an acid (such as oxalic acid), in a suitable solvent or mixture of solvents (such as ethanol and diethyl ether, 111) to ‘produce the monosubstituted hydrazine of Formula Ill. 7 y

Fao _ es ore , 26417 0. ) L ©. Buitable solvents for use in the ° above processes include water) alcohols such as methanol , ethanol, isopropanol and the 11ikeg hydrocarbons such as toluene, xylene, hexane, heptane “and the . 5 likey glymey tetrahydrofurang acetonitrile; pyridine; or haloalkanes such as methylene chloride or mixtures of these solvents. ; ~ Preferred solvents are water, ‘toluene, methylene chloride or a mixture of these solvents. ) | 10 Examples of bases for use in the above

Do process include tertiary amines such as ” triethylamine; pyridines potassium carbonate; sodium carbonate; sodium bicarbonatey sodium } : hydroxides or potassium hydroxide. Preferred bases 1% ars sodium hydroxide, potassium hydroxide or triethylamine, 5 | }

Substantially equimolar amounts of reactants are preferably used, although higher or lower amounts can be used {f desired. ~ 20 ; Benerally, about one equivalent of “base is uséd per equivalent of starting material of Formula

II and V. Where the acid addition malt’ of the . monosubstituted hydrazine of Formula 11 iw. used, one’ additional equivalent of base is used. For 2% example, when substituents A and A’ are the same and a monosubstituted hydrazine is used, about two : equivalents of base are used mince about two equivalents of a suitably substituted " banzoyl chloride of Formula II or V are employed. When 8 LL h 2414 substituents A and A’ are different and an acid addition malt of the monosubstituted hydrazines of

Formula Il] is used, about two equivalents of base are used in B8tep 1 and about one equivalent of base is used in Step 2.

Process A can be carried out at temperatures between about -20°C and about 100°C, preferably between about -%9C and %0° and preferably at about atmospheric pressure, although higher or lower pressures can be used, if desired. ' When the compounds of Formula I have A as 2- pyridyl and A’ and R as defined in Formula 1, they can be prepared by Process B or Process Cs

Process B mc oe me

ZZ .

Cl Base > —C(D)-NH-NHR + A’=C(D)-W =——===>

N Solvent

VI VI

’ : t . CC ~C (0) ~NH-NR-C (D) ~A’

I t :

where W is a strong leaving group such as halo, for example, chloro an alkoxy, for example, ethoxy) a methyl sulfonate (-080,CHx); or an ester, for example, acetate (-0C(0)CH3).

S In Process B, a compound of Formula VI is reacted with a compound of Formula vir in the presence of a base in an {inert or substantially insert solvent or mixture of solvents to produce the desired product of Formula I.

Examples of the compounds of Formula vir which can be used in the above Process B- include ~~ he benzoyl chloride, 2-bromobenzoyl chloride, 3,4 dichlorobenzoyl chloride, 2-iodobenzoyl chloride, ; . 2,4-dichlorobenzoyl chloride, 4-1uorobenzoyl 13 chloride, 2-chloro-3-methylbenzoyl chloride, 2- chloro-4-fluorobhenzoyl chloride and the 11k. The compounds of Formula VII are generally commercially : available or can be prepared by known procedures. a The compounds of Formula VI are prepared from he 20 commercially available compounds by procedures well known to those skilled in the art. BY" way of : : example, a suitably substituted hydrazine (such “as . t-butylhydrazine) is reacted with a pyridyl ester : (such as ethyl 2-pyridylcarboxylate) in an inert or { 2% substantially inert solvent or mixture of “solvents (such as ethanol), with heat, to yield the compounds of Formul a vi (such as. 1-(2- pyridyl carbonyl) ~2-t-butyl hydrazine) . : OE {

LT

Process C + HN-NR-C(0)-A’ Base » nS ~-C(0)-W 8olvent

N

VIII 1X — ® ~C (0) ~NH~-NR-C (DY) ~-A’ . 1 nL - . where W is a good leaving group such as halo, for example, chloroy an alkoxy, for example, athoxy} methyl sulfonate (-0802CHx)3 or an ester, for example, acetate (-0C(0)CHx). - — : In Process Cc, an 1-substityted<1- benzoylhydrazine of Formula IX is reacted with a : ’ LTR . compound of Formula VIII in the presence of a base in an inert or substantially inert solvent or ’ 15 mixture of solvents to afford the desired product of Formula I. se

The compounds of Formula VIII are generally : comsiercially available or can be prepared from commercially available compounds by procedures well known to those skilled in the art as described below. it

, Lo 264117 ’ g Examples of the compounds of Formula 1X which can be used in the above Process C include 1-t- butyl -1-benzoylhydrazine; 1-t-butyl—1-(3-methyl- benzoyl) hydrazine; 1-t-butyl—1-(4-chl orabenzoyl ) ; - 5 hydrazine; 1-t-butyl-1-(2-fluorobenzoyl )hydrazine; 1-neopentyl-1-(4-chlorabenzayl) hydrazine, : and the ’ 3 11 ke. -

Suitable solvents for use in Processes B and

Cc include watery hydrocarbons such as toluene, - xylene, hexane, heptane and the like; alcohols such as methanol, ethanol, { mopropanol and the 11 key { - glyme; tetrahydrofuran; acetonitrile; pyridine; or haloal kanes such as methylene chloridey or mixtures i : : of these solvents. Preferred solvents are water, \ 1% toluene, methylene chloride or a mixture of these solvents. LT “. Examples of bases suitable for use i Process .. B and C include tertiary amines wuiéh an triethylamine; pyridine; potassium carbonates ~ 20 sodium carbonate; sodium bicarbonate; ‘sodium hydroxides or potassium hydroxide. Preferrid banes are sodium hydroxide, or. triethylamine. i . "The above Processes B and C can be tarried out at temperatures between about -%0°C and ; about : 150°c. Preferably, when W is a hale radical, the reaction is carried out between about 0°C and about ) 30°C. When W is alkoxy, the reaction is preferably ; carried out between about 100°C and about 150°C. 2

Wherh W is methyl sulfonate, the reaction is

Co 12 ol

J : Tlie, Le ry Phas uw, oo og Ce A ki gE preferably carried out between about -20% to about 20°c. When W is an ester, the reaction is preferably carried out between about o°c and about 50°C. 3 Preparation of the compounds using Processes

B and C is preferably carried out at about atmospheric pressure, although higher or 1 ower pressures can be used if desired. } ' Substantially equimolar amounts of reactants are preferably used in Processes B and C, although hi gher or lower amounts can be used if desired.

Senerally, about one equivalent of base is used per equivalent of the reactant of Formula VI and VIII.

The agronomically acceptable salts embraced by Formula I of the invention can be prepared by reacting a metal hydroxide, a metal hydride or an amine or ammonium salt, such as a halide, hydroxide or alkoxide with a compound of Formula I having one o 20 or more hydroxy or caboxy groups or reacting a quaternary ammonium salt, such as chloride, : bromide, nitrate or the like with a metal salt of a . compound of Formula I in a suitable solvent. When : a metal hydroxides are used as reagents, useful solvents include watery ethers such as glyme and the likey dioxane) tetrahydrofurang alcohols such as methanol, ethanol, isopropanol and the like.

When metal hydrides are used as reagents, useful solvents include nonhydroxcylic solvents, for

_—_— — - —

SG example, ethers such as dioxane, glyme, diethylether and the 1ikej tetrahydrofuran Ts hydrocarbons such as toluene, xylene, _. hexane, "pentane, heptane, octane and the likey . 5 dimethylformamide, and the like. When amines are used as reagents, useful solvents include alcohols, such as methanol or ethanol; hydrocarbons, auch as 15 toluene, xylene, hexane and the like) tetrahydiofurany glyme; dibxane; or . 10 water. When ammonium malts are umed am reagents, useful 20 solvents include water} alcohols, such as methanol or ethanoly g1yme) tetrahydrofuran or the like. 25 When the ammelpi um’ salt is other than a hydroxide ar alkoxide, an additional bade, such as 19 potassium or aodium hydréxide, hydride, or alkoxide is generally 30 used. he particul ar choice of sblvent will depend on the relative solubiiitias of the starting 3% materials and the resultant salts, ; and slurries rather than wmolutions of certain ; - 20 reagents may be used to obtain the salts. 1

Generally, equivalent 40 amounts of the starting ] } reagents are used and the salt~forming reaction is “Jd carried out at about 0%C 4% to about 100%, ) preferably at about room temperature. | : 2% The acid addition salts of the | present invention can be prepared by reacting hydrochloric, hydrobromic, sulfuric, nitric, phosphoric, acetic, propionic, benzoic or other suitable acid with a ’ compound of Formula I having a basic functional - oo .

) Ie y It group In a suitable. solvent. Useful solvents include water, alcohols, ethers, eaters, ketones, haloal kanes and the like. The particular choice of solvent will depend on the relative solubilities of the starting materials and the resulting salts and slurries rather than solutions of certain reagents may be used to obtain the salts. SBenerally, equivalent molar amounts of starting materials are used and the salt-forming reaction is carried out at from about —10°C to about 100°c, preferably at about room temperature.

The following examples will further jl1iustrate this invention but are not intended to limit it in any way.

Example 4 ~ Preparation of 1-(3,5-dimethylbeiizoyl)- 2 (a-sthylbanzoyl)-i-tert-butylhydrazine.

To a stirred suspension of t-butylhydrazine

Te hydrochloride (1.24 gm, 10 m moles) in toluene (30 ml) at room temperature was added dropwise a 50% . aqueous solution of sodium hydroxide (0.8 am 10 m mole). After 15 min., the reaction mixture was cooled to 5° and a molution of a-ethylbenzoyl chloride (1.69 gm, 10m mole) in toluene (3 m1) and a solution of aguecus 950% sodium hydroxide (0.8 gm, 10 mote) were added dropwise simul taneously from separate addition funnels while maintaining the temperature at or below 10°C. Following the addition, the reaction mixture was warmed to room : 15 : wh pr— _ - Lo een, . 1

Poo : temperature and stirred for 1 hour. The reaction : Co mixture was diluted with toluene and washed with water. The organic layer was separated, dried over anhydrous magnesium gul fate, and the solvent . 5 removed under vacuum to atford a yellow oil which slowly solidified on standing. The product was recrystallized from ether and hexane to yield white crystals. ’ oo ) To a stirred solution of the onobanzoylated compound (2.19 gm., 10m moles) in toluene (30 ml) at =°c, were added dropwise ai mul taneously from : - separate addition funnels, solutions of 345 . dimethylbenzoyl chloride (1.69 gM, 10 ®™ mol es) in toluene (5 ml) and aqueous 0% sodium hydroxide solution (0.8 g) while maintainig the temperature below 10°C. Following the addition, the , reaction mixture was warmed to room temperature and stirred for 1 hour. The mixture was then diluted with hexane and the precipitated product {sol ated by — 20 f11tration. The product was washed with water and hexane and dried. The crude praduct was ’ recrystallized from ather-methanol yielding 1-(3,5- . pencoyt-a- (-ethyibanzayD) “i-LaEE BUTI hydrazine: m.p. 181°C. - .

Example 19 ~ Preparation of 1-t-butyl-1 (4- eample 13 7 TT niorobenzoyl)-2-benzoylhydrazing Co }

To a stirred guspension of t-butylhydrazine : hydrochloride (1.24 gm, 10 m moles) in toluene (30 : 6 ? et

2a ml) at room temperature was added dropwise a 50% aqueous solution of sodium hydroxide (0.8 gm. 10 m mole). After 15 minutes, the reaction mixture was cooled to 57°C and a molution of benzoyl chloride (1.42 gm, 10 m mole) in toluene (5 ml) and a solution of aqueous 50% sodium hydroxide (0.8 am, m mole) were added dropwise simultaneously from separate addition funnels while maintaining the temperature at or below 10°. Following the 10 addition, the reaction mixture was warmed to room temperature and stirred for 1 hour.

The reaction mixture was diluted with toluene and washed with water.

The organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent removed under vacuum to afford a yellow oil which slowly solidified on standing.

The product was recrystallized from ether and hexane to afford white crystals. a : To a atirred solution of the monobenzoyl ated compound (1.92 gm., 10 m moles) in toluene (30 ml) at 5°c, were added dropwise simultaneously from separate addition funnels, solutions of 4- - chlorobenzoyl chloride (1.75 gm., 10m moles) in toluene (5 ml) and aqueous 50% sodium hydroxide solution (0.8 g) while maintaining the temperature below 10°C.

Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hour.

The mixture was then diluted with hexane and the precipitated product isolated by

= wo aig 26417 filtration. The product was washed with Water and hexane and dried. The crude product was recrystallized from ether-methanol yielding 1-t- butyl-1-(4-chlorobenzoyl)-2-benzoylhydrazine as a : +] white powderim.p. 201-204.

Using the same procedure as used in this example, Examples 1-3, 6-14, 16-25 and 38-287 described in Tables 1 and 2 below were also prepared except the benzoyl chloride (Formula II of

Process A) was: 2-bromo—3-methylbenzoyl chloride, oo 2-methyl -3-bromobenzoyl chloride, 2-methyl-3- chlorobenzoyl chloride, 2-methyl~3-f1uorobenzoyl chloride, 2:3-dimethylbenzoyl chloride, 3,5 : dimethylbenzoyl chloride, 2-chloro-3-methyibenzoyl chloride, 2-chloro-4-fluorohenzoyl chloride, 2- chloro-3-methoxybenzoyl chloride, 2,3~dichloro- banzoyl chloride, 2,4~-dichloraobenzoyl chloride, 2-sthyl-3-chlorobenzoyl chloride, 2-f1uoro-3- methylbenzoyl chloride, 2-¢1uoro-3-chlorabenzoyl . - 20 chloride, 2,3-di fluorobenzoyl chloride, 2,6 di fluorobenzoyl chloride, 3-methoxy-4-methylbanzay] ) chloride, 2,3-dimethoxybenzoyl chloride, 2,3-di- - methoxybenzoyl chlorida, 3,4-d1 methaiybenzoyl chloride, 2-bromobenzoyl chloride, a-brdnobeneoyl chloride, 4-methylbenzoyl chloride, 2-chlorabenzoyl chloride, 4-chlorobenzoyl chloride, 2-£1ubrobenzoyl chloride, 4-fluorobenzoyl chloride, 4-1 oidobenzoyl chloride, 2-methoxybenzoyl chloride, 3-methoxy- benzoyl chloride, 4-wthylbenzoyl chioride, or 18 ee”

oo ez benzoyl chloride, and the 4-chlorobenzoyl chloride (Formula V of Process A) wast 2-bromo—-4-chloro- benzoyl chloride, 2-bromo-4-f1luorobenzoyl chloride, 2,4-dibromobenzoyl chloride, 3,5-di bromabenzoyl } 9 chloride, 3,%5-dimethylbenzoyl chloride, 3-methyl - s-chlorobenzoyl chloride, 2-chloro-4-broficbenzoyl chloride, 2—chloro-S-methylbenzoyl chloride, 2-chloro-4—fluorobenzoyl chloride, 3-chloro-4- fluoragbenzoyl ‘chloride, 2-1 odo—-4~chlorobenzoyl chloride, 3—-ipdo-4-chlorobenzoyl chloride, 2,4-di-

N chlorabenzoyl chloride, 3,4~-dichlorobenzoyl chloride, 3,5-dichlorobenzoyl chloride, 2-#1uoro- a-chlorobenzoyl chloride, 2,4-difluorobenzoyl chloride, 3,4-difluorobenzoyl chloride, 3,%-di- i3 fluorobenzoyl chloride, Z-bromobenzoyl chloride, 3-bromobenzoyl chloride, a-bromobanzoyl chloride, 3-methylbenzoyl chloride, 4-methylbenzoyl chloride, 2~chlorobenzoyl chloride, 3-chlarobenzoyl chloride,

A-chlorobenzoyl chloride, 3-ethylbenzoyl chloride, 2-fluorobenzoyl chloride, 3-f1uorobenzayl chloride,

A-fluprobenzoyl chloride, 2~1odobenzoyl chloride, 3~-iodobenzoyl chloride, 4~{ndobenzoyl chloride, - benzoyl chloride, or vinylacetyl chloride.

Example 27 — Preparation of 1-t-butyl-i-benzoyl-2- apyidinecarbonylhydrazine.

To a suspension of t-butylhydrazine hydrochloride (9.9 gm, 0.794 mol) in absolute ethariol (50 ml) was added SO0% aqueous sadium fo nn JeflE

FO hydroxide (6.33 gm). The mixture was stirred and warmed up while ethyl picolinate (12.0 gm was added dropwise. The resulting mixture was allowed to reflux for about 3 days. After cooling, water was added and the product extracted with methylene chloride, The organic layers were washed with water and dried over magnesium sulfate. .

Evaporation of solvents afforded {t-butyl -2- (2 pyridinecarbonyl) hydrazine as yellow oil which . 10 solidified on cooling. , . : . A solution of the 1-t-butyl-2-(2- pyridinecarbonyl) hydrazine (1.0 gn. 0.00818 mol.) in 20 ml. of toluene at 23°C was treated sequentially with 350% sodium hydroxide (1.3 gm) ‘and benzoyl chloride (0.728 gm). The mixture was stirred overnight. The solids were remaved by filtration and washed with water to yiwld 1-t- : butyl ~2-(2-pyridinecarbonyl)-1-benzoylhydrazine: : m.p. > 200°C. | a = 20 Examples 26 and 28-34 were prepared - in the sane manner except instead of using |’ Benzoyl - chloride, 4-fluorobenzoyl chloride (x. 26) , 2~ bromobenzoyl chloride (ex. 28), 3,4-dichlorobenzoyl chloride (ex.30), 2-iodobenzoyl chloride (xs 31, 2% 2,4-dichlorobenzoyl chloride (ex. 32), 2-chlaoro-5- methylbenzoyl chloride (ex.33) and 2-chlorom4- fluorobenzoyl chloride Ca. 34) were used.

Example ‘37 - Preparation of 1-t-butyl-1,2-bis(4- chiorcbenzoyl hydrazine bnbeibutuiaiet An Anti Co

RE 20 So fn suspension of t-butylhydrazine hydrochloride (12.5gm, 0.1 mole) in toluene (100 ml.) at 0-5°C was treated slowly with 1 equivalent of sodium hydroxide solution, prepared ¢r-om diluting 8 gm of 50% Sodium hydroxide commercially available solution to 20 ml with water. At © “to 50°C with mechanical stirring, 2 equivalents of 4- chlorobenzoyl chloride (35.9 gm, 0.2 mole) and 2 equivalents of B8Sodium hydroxide (1&6 gm of 50% sodium hydroxide diluted with water to 40 ml) ere added dropwise sepanately and simul taneously from dropping funnels. The exothermic reaction was cboled down by an icewater bath through the entire addition. After the addition was completed, the resulting suspension was stirred at room temperature for one hour. The white precipitate was collected by suction—filtration and washed with a small amount of toluene and 100 ml of water.

The material was air-dried, then crystallized from 95% aqueous methanol to afford 24.45 gm of 1~t- 4 butyl—-1,2-bisg{4-chlorobenzoyl hydrazine as needles: y m.p.246-248°C,

Additional product can be obtained by concentrating the mother liquor of crystallization.

TABLE 1 | } , 0 0 Co : . 7 an ' 5 i CH3~C—-CHx y os of

Example A A’ 1 4-Med 3-Med 2 4-Me® 3,5-Megh 3 3-Me® o = 4 _ A-EtQ 3,5-Meod © 2,3-MesDd 2-Bri & 2,3-Mep0 2,4-Cle0 7 2, 3-Meo0 3,5-MeoD 8 2,3-MeoD 3-Mel . 10 9 2Me ,3C10 o 2Me ,3C10 2C1 ,4F@ 2 : 11 2C1 , 3Me00 3,5-Meol 12 AELD CHa (=H) CHE 13 o 2c10 = 193 14 @ 3,4C1,D * 1s 2 ac1e KE 16 ® es - 17 2 4FD a : . 18 @ 2Br , 4F0 ae 19 @ | 2BrB i - } 20 4FQ AFD i :

C21 2F@ 2FD 0 : © 22 acia Icio ey 23 2,6F 50 2,4C150 Le 28 24 2,6F 20 3,5F20 : - 2 CHgC (=CH2) CHz 26 2-pyridyl AFQ oo

2a

Example Ax ax 27 2-pyridyl @ a 28 2~pyridyl 2Br@ 29 @ 2C1 ,AF0 30 2-pyridyl 3,4C12 31 2-pyridyl 210 32 2-pyridyl 2,4C1 0 33 2-pyridyl 2C1 , SMe? 34 2-pyridyl 2C1 ,4F0 as 2,3Meo0 CHZC (=CHy) CHx # Q is phenyl. : .

Me is methyl : . Et im ethyl

MeO is meathouy.

: TABLE 2 a oN & 3)

A oo : 5 CH =e C——eCHy (A)

CHx

Example A \ A’ 34 H, - 31,4C1 37 a acl 38 2C1. 2C1

To 10 39 aMe acy 40 H 3c1 a1 H 3Me ; ) a2 H 2F a3 H 2,4Cly 44 acl H ; 43 H 3,58Clp ab 2c1 H

Co a7 ac 34013 as 2C1 34615 a9 aMe 3.4019 50 ame 2,401 51 aMe 3,5C15 52 aMe 2c1 53 4Me 4F 54 act 3Me - 59 H | 4Br

S56 H 3Br | :

oo 2ay)7

Example A AL 57 AEL H 56 H 2C1,4Br 59 H 2,4Bro 60 H 3, 5Me 61 ach 2c1 &2 ac 3,%Clo 3 acl 2,4C1 5 54 AMe aC 55 H 21 bb H 31 67 AEL Me 68 AEE ac1 69 2Br Ho 70 3,4(Me0) H 71 H 3Et 72 AEL 3Br 73 4EL 21 . 74 2Br 2Br 75 2EL 3EL - Th AMe Br 77 H ar ’ : 4Me 3EL 79 AEE 2,4C15 2% 80 2C1 Me a1 2C1 2Br 82 2F act a3 2c1 2,4C17 84 201 3C1 as 2,6C19 H i

Ce Ceram i egy . Example A A’ 86 | 21 aw 87 2€1 4Br 8s 2C1 ac1 89 21 2F 90 3Me0 3Me ) 91 3Me0 Ho

Bh 92 3MeO acl : 93 3Me0 3,401 94 2Me0 H 95 2MeD 3Me 96 2Ma0 3,4C1 3 97 2Ma0 act 98 2,6F5 3,4Cly ; 1% 99 2,6F3 3Me 100 act 3,5Mey 101 3Me0 3,5Meg 102 ac1 2 103 4C1 aF ; 20 104 EL . 2Br En : 105 2,6F3 2€1 Lo 106 2,6F2 3c 5 : 107 2,6F3 acl 5 108 2,6Fy 3,5Mey 109 aE H » wo iio at 3,sc15 © 11 - 4C1 2F _ 112’ | AE 3,4C19 So 1s oo Et 2F 114 ' 4Br 4Br

Fy

CE 26 - )

oo To ougp

Example A Aa. 115 2,6F 3,5Cls 116 2F 2Br 117 2F 3Me 118 2F H 119 2Me , 3C1 Me 120 4Br H 121 2,3C1p 28r 122 2,3C15 H 123 2F 3, 5Me 124 2,3C15 3Me : 125 H 3C1,4F 126 acy 3C1,4F 127 2,3Meq 3,4Clp 128 2,3Mes 3c1 129 2,6Fp 2Br 130 2Me,3C1 3, SMe 131 2Me, 3C1 3C1,4F

CC q32 2,3Men C1, 4F . _ 20 133 AEt 3C1,4F 134 2C1 ,6F Me o 138 2,3(MeD) 2 Hoo 136 2,3 (Me) 2 Ac1 137 2,3 (Me0) 2 2Br 138 2Me , IF Ho . 139 2Me , IF 3Me 140 2C1 ,&F H 141 2C1 , 6F AF 142 201, 6F 2,4C12 143 2,3F 2 Mo

Ro Ya I: 06417.

Example a oar 14a 2,3C15 3, smal 145% 2,3Clo 2,4C15. tas 2,3C15 3,501 5 147 2,3C1 5 acl 148 2,3F5 28 149 2,3Mes ac1 150 2,3Mey 2,4F 5 151 2Me , 3C1 2,4C13 152 aEt 3,5F5 153 2,3Men 21 154 2,3F5 Me : 183 2,3F5 3,SMey. 156 2,3F 2,4C15 157 2,3Me, H 198 2C1 ,3Me 2,4Cly 159 2C1 ,3Me _H Co 160 2C1 ,3Me 3Me Co 161 2C1 ,3Me 3,5Mey - 20 162 2C1,3Me 3,5C15 163 2,3Mez 2c1 164 2,3Mes 3,8c15 © 16% 2,6F 2 3C1,4F 166 H 3,4F5 2% 167 acl 3,56 148 2,3Me; 3,53 169 2Me , 3C1 3,5F 170 H 3,5Fz ii : 171 | 2Me , 3C1 3,5C1 5 172 28r 3,5Meg oo 3 28 3 & AML Gag cll}

Example n a’ 173 20, 3Me 3) 174 CR H 175 PHer , ICT ac 176 [Mey IC] 1F 177 “Me, 300 AR 17a 2C1 , IMen AMen 179 201 Fed H 180 DCL, Men PoC) 2 181 AMel, MMe AMe 182 2Me , 3Rr + 183 Me, IBr FMe 184 ZMe , Pr ACT 185 He , IR 2,401 2 186 IMex(3, AMe Zhe 187 Med, AMe 2,0) 188 2Et ,3C1Y H 189 Et, 301 2,4C1~ 120 2R IMe 121 2Rr 2,1C1o 192 2F 4 3Me H 193 ?F , AMe 3Me 194 ZF ¢3Me 3,4C1 A 195 2F , 3Me 2,401 196 2F , 3Me 4F 197 PF, Me act 198 2 Meo JEL 199 2F Me 3,5Me 200 ZRr CL 201 2h 3,501 3? | PS,

BAD ORIGINAL J

L

. . Ce ; we -

Example A A’ 202 2Br , 3Me | 3,5Mes 203 2Br ,3Me 2,4Cl 2 204 2Br , IMe Me 20% 2Br , 3Me 3,5Clz 206 2Br , 3Me 2Br 207 2Br , 3Me acl 208 2Br , 3Me H 8 209 2Br ,3Me AF 210 2Br , SMe 2,4F 3 : 211 H 2,4F 212 2,6F 5 2,4Fp

Co 213 2,6F2 2C1 , 4F : 214 243Me; 2C1 ,4F 1% 215 2C1 ,3Me0 2Br 216 2,3Meas 2Br ,4F oo 217 2F ,3C1 H : 218 2F,3C1 3,5Mes 219 2F ,3C1 2,4Clp. 220 2,3Meo 3,5Bro 221 aEt 3,58rp 222 H 3,58rg 223 IMeD 20 224 ~ 3MeO 2,4C15 2s 41 H 226 41 2,4Cly 237 a1 3, SMe 298 4Br 3Br i ‘229 ABr 3,4C15 230 4Et 1 go

ZCI}

Example A 0’, 231 AR. 3,5Me 232 apr Me 233 ?, ICL CL, AF 2734 Me, 301 a 23% THe, 30 201 236 “Me, 301 TH AF 237 “Me, 301 2F 40] 238 2, Ie AF 239 EE RGM 240 Br ar 241 oF 24 AF 242 oF 201, AF 2473 oF 2,014 244 H 2F, 401 245 2c 2C1 , AF 246 act 201 AF 247 NEL 201, AF 248 ar ach 249 2y6F AF 250 2, 3Men Wr 251 or 24 AF 252 21 AF 253 2,0 (Mel) 3, Gen 254 7 Mes Me, SC 25% AL Ae, SC \ 256 H 21,401 257 1 ZBr, AC 3 } .

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\

Coa

Insecticidal Examples

The compounds of Formula 1 were tested for their insecticidal activity using the following 3 — a) Rice Stem Borer —~ Chilo suppressalis Wik.) - foliar application. - Rice seedlings (var. Nippon-bare) at the budding stage were dipped in a 38 parts per mi1110n : 10 (ppm) test solution of each compound. (The test solution was prepared by dissolving the compound in a solvent of acetone and methanol (111 patio), adding water to give a acetone: methanol 1 water system of 5:15:90 and then a surfactant was added. 19 A fet mixture of an alkylarylpol yetheral cohal (mold under the trademark Triton " X-15%) and a modified phthalic glycerol alkyl resin (sold under the trademark Triton R B-19354) was utilized at the equivalent of 1 ounce per 100 gal. in the test = 20 solution as a surfactant. Unless usage of a formul ated product has been speci fied, test i : solutions of compounds were prepared in 11ke manner al though the concentrations may differ among the insect species tested.) When the plants ware dry, 23 each seedling was placed in a Petri dish and - infested with ten second instar larvae of the rice stem borer. The dish was covered and held for six days after which time the percent mortality, based . - } , 32 eo Te 3 upon dead and moribund larvae, was determined. The averaqgn percent mortality Over three such replicates per compound i= shown in Table 3. t) Ricmhappers — faliar application.

S Frown Rire Flanthopper - Nilaparvata Jugens (Stal.)

Gr een Rice lLeafhopper - Nephotetti: cincticeps (Uhl.

Rice seedlings (var. Nippon--hare) at the 4- leaf stage and maintained in glass heakers were sprayed with a A400 ppm test solution of each compound. When the spray had dried, pach beaker was infested with a minimum of 100 second instar nymphs of either the green rice leafhopper or the brown planthopper (BRFH) and covered with a cloth.

Eight days after infestation the number of insects alive was determined. The percent mortality was calculated on the basis of an initial population of 100 arganisms. The sverage percent mortality over two such replicates per compound is shown for each test species in Table X. - re ~~ a3 TT a0 ORIGINAL J \

TABLE 3 wo ;

Percent Mortality -

Rice Stem Brown Rice ‘Breen Rice

Borer Planthopper Leafthopper

Example (38 ppm) (400 ppm) - {400 ppm) 1 a7 0 as 2 100 5 . 40 ; 3 80 5 am 4 100 0 en 5 100 0 BN 2% 6 93 5 1m 7 100 0 13 e 80 ) 7S 9 87 10 30 10 87 10 :T] 11 80 0 =0 12 - - Lo. 13 100 5 58 14 73 0 15 = 15 80 10 "om 16, 73 0 . 60 17 e7 0 es 18 93 10 2s 13 87 0 80 20 93 5 1s 21 100 0 a8 #2 Not Tested. 34 CL # ars GAS

2+

Percent Mortality “hice Stem Frown Rice Green Rice

Bor er "lanthopper L.eafhopper

Example (8 ppm) (&HO0 pron) (600 ppm) - — LTT Ea TTT ; 23 23 3) 10 : en 100 0 15 : 29 I 0 92 ob 80 35 A40 27 100 0 &5 28 P73 5 60 ec) Rice Leaf folder or Rice |. mafroller — Cnaptha - locrocis medinalis (Guen.)

Five rice leaf hlades (variety Finmazel) were soaked for 30 seconds in a test solution containing 100 ppm of active ingredient of the compound of example 4, prepared from 10% aqueous flowable preparation of the compound. When dry, the rice \ blades were cut and placed on moist filter paper in ° a Petri dish and infested with five third instar rice leafroller larvae. The percent control was determined & days after infestation and the compound gave 100% control, i.e., all larvae had died. od) Rice Stem Rorer — Chilo suppressalis Wik.) ~—

Systemic artivity.

Rice plants (variety Nippon-bare) in the 8 leaf stage were grown in 1/5000 are Wagner pots.

Compound of example 4 formulated as 239.7 grams per liter aqueous flowable (ZF) preparation was introduced onta the 3 om deep water surface in thease pots to provide a concentration sgquivalent to a5

BAD ORIGINAL 2

Ocetit 1200 gm (a.i.)/ha (hectare). Eight days after - treatment each pot was infested with 30 first } instar rice stem borer larvae. Ten days after : infestation, the plants were examined for the nN presence of live larvae. The percent control : averaged over two replicates is shown and reflects carrection for natural mortality as per Abbott's formulal, The compound of example 4 resulted in 97 percent mortality (corrected). - a) Southern Armyworm - Spodoptera eridania - Cv (Cramer) - foliar application.

Leaves were placed on moi stenaed places of filter paper in Petri dishes. The leaves were then ; - | © sprayed with a 400 ppm solution of a test compound 13 . using a rotating turntable and allowed to dry. The dishes were then infested with 10 third instar : . larvae of Southern armyworm and the dishes were © Eovered. The percent mortality for the armyworm — evaluations were determined 94 hours after ‘ treatment. Evaluations are based on a scale of 0- “100 parcent in which 0 equals no activity and 100 . | gquale total kill. ‘

CT bate, me. A Method of Computing the

TEENIE san tecticide. I. Econ. Entonal i.e. Br XK 100 = X corrected mortality where X = average %X alive in the untreated check replicates .and

Y = average % alive in the treated replicates. oo 3b : ify fd hei :

Jer}

Compounds of eramples 1-33, 35-69, 71-74, TH- 23, 95, 27-252 and 254-257 all gave 100 percent controls the percent control of evamples 34 and TO were 103 examples 77 and 94 were 903; and examp) es 96 and 257 were 30.

This artivity against Southern armyworm, A

Lepidoptera, is considered indicative of activity against rice Lepidoptera in view of the data presented in Table 3.

Toxicology Fuxamples

A portion of the compounds used in this invention were tested to determine their toxicity against several different species of animals. The procedures and their results are given below. All these results are indicative of low tonicity. a) Nmes Test

Several of the compounds used in the present invention were tested in the Ames Test, a microbial mutagenicity assay. The compounds were tested against Salmonella typhimurium strains TA 1535, TN 1537, TA 98 and TA 100 according to the procedure described by Ames, et al., "Methods for Detecting

Carcinogens and Mutagens with the

Salmonella/Mammal i am—-Microsome Mutagenicity Test",

Mutation Research, 31:347 (1975). The microsomal extracts were S-9 liver extract fractions from

Aroclor 1254-induced rats. The microsomal extracts were tested with a positive control, which was a compound whose mutagenic activity required 37 err meta———r— —-

BAD ORIGINAL J

“Uy metabolic activation prior to use. The purpose of oo the positive control which was run with caih ansay, ; was to ensure that both the organism and the 8-9 A liver extract were functional. The max i mum : concentration of the test compounds was 5,000 micrograms of active ingredient per ‘plate.

Examples 1, 2, 4, 6-9, 14, 15, 17 and 19 were tested and all tested negative, i. e., demonstrated no mutagenic activity. oo b) Rats, Oral Toxity

The acute oral tonicity of example 4 was asswesad in male Crl:CD BR rats. The solid test substance was dispersed in corn oil and administered as a single oral dose by gavage (20 ml kg) to a group of 10 male rats at a dosage of %.0 gm/kg. A control group of rats received corn oil in the same manner. The rats were obasrved for 14 days. The rat oral LDsg (lethal dose required to kill fifty percent of the rata) for both . 20 examples 1 and 4 is greater than 5600 mg of ¢ompound per kilogram of body weight. Po i Examples 2, 6-9, 14, 13 17 and 19 vere run in the same manner except a single dose of 10 ml/kg was administered, a dosage of 3500 mg/kg was used and there were & male rats per group. All of these © gompounds have rate oral LD=o values of greater than 500 mg/kg. | =n ’ c) Rats, Dermal Toxicity ‘the acute dermal toxicity of Example 4 was assessed {fn . male CrliCD Br rats. | The test

Cp | | 38 BN fr, apne oon - Co ’ ) ¥ oc substance, moistened with 0.85% maline (1:3 w/v), was applied to the clipped intact skin of six male rats at a dose of 5.0 gm/kg body weight. The application sites were covered with impervious cuffs for a period of 77 hours, after which the cuffs ware removed and the sites wiped with water - snaked paper towels. A conteel group of six male vate were wrapped with cuffs in the same manner hut received no test substance. The rats were observed far 14 days. fhe rat acute dermal LDsq for example 4 was greater than 5,000 mg/kg.

Examples 1, 2, 6&9, ta, 15, 17 and 19 were tested in the same manner pucept the dnse of thee compounds were 200 mg/g. ALl had LDDs values of greater than 200 ay / kg. 3d) Bobwhite BDuail

Example A was tested to determine the lethal dietary concentrations needed to kill 50% (LCsa) of

Bobwhite quails. The compound was administered in the diet to groups (10 per group) of young quail (13-14 days ald) at concentrations of 312, 625, 1,280, 2,500 and 5,000 ppm active ingredient for five days fnllowed hy three days of feeding on a control died (recovery phase). The control popul ation consisted of five separate groups of ten qual ls pach. Mhiservations for mortality, mori bundi ty , and signs of intoxication were made daily. Noi mortalities were recorded in the test groups for the compound of example 4 or control

Co i. 3g ~ “al

BAD ORIGINAL J

J

;

) ni 2¢ YI} : groups throughout the study. The 8 day dietary )

LCxo of example 4 was determined to be greater than %,000 ppm active ingredient. ®) Mallard Ducks . = The compound of example 4 was tested to determine its LCso in a ten-day dietary study of

Mallard ducke. The test was run using the same procedure as for the Bobwhite quail except the ducklings were 7-8 days old. Two ducks from group fad S,000 ppm of example 4 died. The 10 day dietary LCxo of example 4 was greater than 3,000 ppm active ingredient. ¥) Daphnia magna

The susceptibility of Daphnia magna, a water flea, to example 4 was measured in 48 hour static water toxicity tests. The study was conducted in vessels each having a different concentration of the test compound, also included were water and solvent, 0.5 ml. per liter of dimethyl formant de, = 20 controls. Example 4 was tented at concentrations ot 1.0, 1.8, 3.2, 5.6, 10, 18, 32 and 50 ppm. The ’ taste, including controls, were run in duplicate.

Ten daphnids were introduced to each vessel. Lo

Concentrations of test compounds of 1.8 mg/l and ’ ’ higher resulted in a precipitate. The .48 hour : effective concentration to have an effect on 50% of the daphnids was estimated to be for example 4 close to its solubility Limits, f.@., between 1.0 and 3.2 mg/l. a0 -

QC g) Rainbow Trout and Bluegill) Sunfish

The static water R6-hour acute tomiecity of rainbow trout (Salmo gairdneri) and bluegill sunfish (Lepomis macrochirus) to ouample 4 was determined. The studies were conducted at concentrations of 0.32, 1.54, 1.0, 1.8, 3.2, 5.6 and 100 mg/l of example 4 with ten fish of each tyne per cnncentratian, pueept the 100 mg/l concentration which wan run in triplicate.

Concentrations of example 4 of 1.8 mg/l and higher resulted in a precipitate. The studies also includerd water controls and solvent, dimethyl formamide at 0.1 mg/l, controls each with ten fish

LI per vesse) Thirty minutes after the test compounds were added to the chambers, the fish were added by random assignment. The 6 hour LCsp values for example 4 for both rainbow trout and bluegill sunfish were greater than 100 mg/l.

Example A was alno tested against carp and exhibited low toxicity.

The insecticidal compounds used in the present invention may he used tn low dosages in controlling pests. The rnsage depends on a variety 2% of factors, for example, the subhatance used, the oo vind of pest, the formulation used, the state of the crop infected with the pest and the prevailing weather conditions, In general, for the control of poate in rice, a dosage corresponding to from about 10 gm. to about 10,000 gm nf the active substance

EE

: a1 \ ) v

BAD ORIGINAL J oo fies Gey Co per hectare may be used and from about 350. gm. to : about 1,000 gm per hectare of the active sistance oo is preferred. wr -

The compounds of Formula I can be utilized in the form of compositions or formulations. In these } compositions and formulations, the active substance : is mixed with conventional inert TR plant : compatible and/or pesticidally inert) diluents or extenders such as solid carrier material or liquid carrier material of the type usable in conventional compositions or formulations. 1¢ desired, vo adjuvants such an surfactante, stabilizers, . antitoam agents and antidrift agents may also be combined. Examples of composi tions and formulations are aqueous solutions and dispersions, dusting powders, granules, oily solutions, oil dispersions, pastes, wettable powders, eniil ei fiable : concentrates, flowables, baits, invert ehulsions, aerosol compositions and fumigating candles.

Compositions and formulations are prepared in a ; known manner, for instance by extending the active ) compounds with conventional dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier’ vehicle assistants, e.Qny conventional surface—-active agents, {neluding emulsifying agents and/or digpereing. agents. - - i The compounds used in the present invention oo may be ‘enployed alone or in the form of mixtures . with one another and/or with such solid and/or }

EE \

0 a liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection gent ey meh AS ather arthropndicides, necarb ord don, fungicides, pi hactericides, radontirides, herbirides, fertilizers, growth-reag:’ ting agente, synergists, etc., if desired, or in the Form nf particular dosage preparations for speci fic applications made therefrom, sme hy as aolutione, amu) oi ons, suspensions, powders, pastes and granties which are thus ready for ase,

Tn the compositions of the present invention the active compound is generally present in an amount substantially between about 0.0001 percent 13 and 9% percent by weight and preferably between about 1% and 75% by weight. Mixtures suitable for direct application or firld application generally contemplate those in whirh the active compound is present in an amount substantially between about 0.0001 percent and 5 percent, preferably between about 0.001 percent and 3 percent, by weight of the mixture.

The present invention contemplates overall compositions which comprise mixtrres of a conventional dizpersible carrier such as (1y a disperaihl= inert, finely divided carrier solid, and/or (PM a dispersible carrier liquid such as an inert organic solvent and/or water, preferahly including a surface-active effective amount of = 473 (err .

BAD ORIGINA- 9

- | Cn DeHitete

RIVET : hry 5 4 Fp ~ | 2 20417 |» carrier vehicle assistant, (e.g., a surface-active agent, such as an emulsifying agent ‘and/or a dispersing agent), and an amount of th@ active : compound which is effective for the . purpose ! a ’ i 3 desired. : : . 2 i + The active compounds can be applied as sprays \ “in - by methods commonly employed, such as conventional high-gallonage hydraulic sprays, low gallondge i sprays, ultra-low-volume sprays, airblast sprays, - . 10 asrial sprays and dusts as is known in the: art.

The active compounds can al so be strewn - mechanically or by hand as dusts or granules, E . r+ Furthermore, the present {rivention ! contemplates methods of selectively killing, A v } i «“ >. 19 combating or controlling pests, which comprise ; applying to at least one of (a) such pests and (b) . the corresponding habitat thereof (i.e., the locus to be protected, for example, to a growing chop or } ; " “a oo if to an area where a crop is to be grawn) a i

Pea ¢ \ 20 correspondingly combative or toxic amount Hie. , a # pesticidally effective amount) of the particular Co active compound of the invention alone or ‘together Cy : lo Ab Cur Cd with a carrier vehicle as noted above. a oo Coal

LO Co i : 5 4

It will be realized, of course, that the 3 2% concentration of the particular active Eampound i utilized in admixture with the carrier vehiEiw will 3 depend upon such factors as the type of equi pment employed, method of application, area to be oo i treated, types of pegts to be controlled and degree a 1 aA b vr : . be

Lo { J . GT J {

Ll Cb oi

9c it of infestation. Therefore, in special cases, it is possible fo go above or below the aforementioned concentration ranges.

In addi Lion to the Aforementioned ingredients, the preparations, according to the invention, may also contain other substances commonly used in preparations of this lind. For example, a lubricant, such as calaium atearate or magnesium stearate, may be added to a wettable powder or tn a mixture to be granulated.

Furthermore thers may, for example, be added "adhesives" such as polyvinylaloobol, cellulose derivatives or other colloidal materials, such as casein, to improve the adherence of the pesticide to the surface to he protected.

The compounds of the invention are also useful to control insects in seeds, generally by applying an effective amount of the compound to the - surface area of the seeds to be treated. This may be accomplished hy varying means common in the art, such as slurrying, soaking, dusting, spraying and

J the like. !, Compositions and formulations according to ; the present jnvention may also include known 25’ pesticidal compounds. This expands the spectrum of / ! activity of the preparations and may give rise to dynergi sh. ’ , ba i» } ; pp \g AD ORIGINAL J ro ! ' oo ‘

Claims (1)

1. ASN SG FL | Wo oer, is RE 26417 * Ll . CLAIMEB Fo What ie claimed is! on Ye A method of controlling insects in the : 5 vieinity of a rice field comptiming contseting to : the insects an inmacticidally-effective amount of a compound of the formula: A — EE \ R ’ : wherein R is tert-butyl or neopentyl; LL : A is 2-pyridyl, phenyl or phenyl subitituted . with one or two substituente each independently = salacted from the group consisting of 2- ok. d-hale, 2,8 or 2,6-dihalo, d-(C4-Cz)alkyl, 23541 (Cy - Cy jalkyl, 2-{Cy-Cy)alkyl-3-halo, 2-halb:3-(Cy- Cp)alkyl, 2,3-di(Cy-Cz)alkoxy and 2- or’ 3-(0y- | ) I; Cp )alkoxy} A' ie 1-mathylethenyl, phenyl of: ‘phenyl - substituted with one or two substituents each ) independently selected from 2-, 3-, or ;, d-halo, ’ : 3,6% 3,4- or 2,4-dihalo, 3-(Cy-Cz)alkyl, 3,821 (C4 - Ca)alkyl, 3-(Cy-Cp)alkyl-6-halo and 2-hatozh{Cy-Ca) alkyl, provided A and A‘ are not both phaiiy1) and agronomically-acceptable salts thereof. ia

   : a. The method of claim 1 wherein R ia tart- CL : butyl, A is 2-pyridyl, phenyl or phenyl eubbtituted ) 28 with one or two substituents each indepsdantly Co gelactad from the group consisting of 2- or d<hald, : 1 | oo

   SC fig i 26417 P 2,3- or 2,6-dihalo, 4-(Cy1-Cylalkyl, 2,3-di(Cy-~ Cyr)alkyl, 2~{(Cy~Cp)alkyl-3-halo, 2,3-d1(Cy~ Cz)alkoxy and 2-halo-3(Cy-Cpylalkyl; A' is phenyl or phenyl substituted with one or two substituents gach independently selected from 2-,3- ar 4-halo, 3,6- 3,4- ov 2,4~dihalo, 3-(Cy-Chlalkyl, 3,56-d4i(Cy~ Colalkyl, 3-(C3;-Czlalkyl-56-halo and 2-halo-6-(Cy~ Czl)alkyl, provided A and A' are not both phenyl; and agronowically-acceptable salts thereof.

   3. The method of claim 2 wherein A is phenyl or phenyl substituted with ona or two subatituents each independently tietected from the group congisting of d-halo,4-(Cy-Co)alkyl, 2,3,-di(Cy~- Crlalkyl and 2,6-dihalou; and A’ is phenyl 18 substituted with oae ovr two substituents each indepandently selected from the group consiuting of 2-halo, 2,4-dihalo, 3-{C;-Cplalkyl and 3,5-di(C;~- Cplalkyl; and agrotnomlcally-acceptable salty thereof.

   4. The method of claim 3 wherein A is phenyl substituted with 4-methyl, d-ethyl, 2.6-difluovra or 2,3-dimethyl aud A' is phenyl substituted with 2- chloro, 2,4-dichloru, 2-¢hlora-4-fluoro, 3~matlhyl or 3,5-dinethyl; and ugronounlcally-acceptable salts therwof.

   5. The wethod of «claim 4 wherein the compound is, i1-(3,5-dimethylhenzoyl }-2-(4- ethylbenzoyl)-1-tert-butylhydrazine. ’ BAD ORIGINAL dD L :

   ie {IF ' 26417

   .

   0. The method of claim 4 wherein the compound is 1-(3-methylbenzoyl)-2-(2,3- dimethylbenzoyl)-1-tert-butylhydrazine.

   - 7. The method of «claim 4 wherein the ‘ 5 compound ig 1-(3,8-dimathylbenzoyl }-2-4(4~ + methylbenzoyl)-1-tert-butylhydrazine.

   . 8. The method of claim 4 wherein the compound is ~{{2-chloro-4-fluorobenzoyl )-2-~ benzoyl-1l-tert-butylhydrazine.

   9. The method of claim 4 wherein the compound is t-(2.,4~-dichlorubenzoyl)-2-(2,6- difluorvbanzoyl)-1-tert-butylhydrazine.

   10. The method of «claim 1 whersin the compound is applied to the rice field at a rate of ls about 10 grams to about 10,000 grams per hactare.

   11. The method nf claim 6 wherein the compound {is applied to the rice field at a rate of about 10 grams to about 10,000 grams per hectare.

   12. The method of claim 4 wherein the compound {es applied to the rice field at a rate of about BO grams toa about 1,000 grams per hectare.

   13. The method of claim 8& wherein the compound li applied to the rice fiald at a rate of about &0 grams to about 1,000 grams per hectare.

   14. The method Of claim 2 wherein the insects are members of the itnseact ovdars Lepidoptera and Homoptera.

   16. The method of claim 14d wherein the insects are frow the ovder Lepidoptera. ) orn CRIGINAL )

   _.

   Ite It 26417

   16. The method of claim 16 wherein the insects are rice stem horers of rice leaffolders.

   17. The methnd of claim 16 wherein the ingectrs are rice leaffolders. 18, The mathod »~f claim 14 wherein the insects are from the order Homoptera. 19, The method of claim 18 wherein the insects are green rice leafthoppers.

   20. An inrpacticidal compertition for vee in rice fielde comprising a» arrier acceptable for ure on rice and an insecticidally-effective amount of a conpound of the formula: Co Al —NH—N _h — A’ R wharein R is tertbutyl or nropentyl; 1h A is 2-pyridyl, phenyl! or phenyl substituted with one or tuo zubrtituents each independently selected from the group consisting of 2- or 4-halo, 2,3- nr 2,6-dihale, 4-(Cy-Cplalkyl, 2,3-di(Cy- Co)alkytl, 2-{Cy~Cq)alkyl-3-halo, 2-halo-3-(Cy ~ Cplalkyl, 2,3-di(Cy-Cp)alkoxy and 2- or 3-(Cy- Ca)alkoxy; A’ is l-meathylethenyl, phenyl or phenyl substituted with one nr two substituents each independently selected from 2-, 3-, or 4-halo, 3,5~ 3,4- or 2,4-dihalo, A-(Cy-Ca)alkyl, 3,5-di(Cy- Colalkyl, 3-{Cy-Co)alkyl-65-halo, 2-halo-5-(Cy~ Chr)alkyl, provided A and A’ are not both phenyl; 4 | - a0) as orn Of) — =

   Dery 26417 ' ‘ and agronomically-acceptable salts thereof .

   21. The insecticidal composition of claim 20 wherein R is tectbutyl, A is 2-pyridyl, phanyl or phenyl substituted wlth one ot two substituants each independently seiected from the group consisting of 2- or d-halo, 2,3- at 2,6-dirhalu, 4-(Cy-Crlalkyl, 2,3-31(Cy-Cylalkyl, 2-(Cy C3) alkyl-3-halo, 2,3-di(C-Cylalkoxy and 2-halo-3-~ (Cy-Cplalkyl; A’ is phenyl! or phenyl substituted with one or two subgtituents each Independently selected from 2-, 3-, of d-halo, 3,5- 3,4- or 2, 4-dihalo, 3-(C;-Cplalkyl, 3,5-di(Cy-Cp)alkyl, 3- (Cy-Cylalkyl-56-halo and 2-hala-5(Cy~-Cphlalkyl, provided A and A' ace not both phenyl; and 156 agronomically acceptable salts thereot.

   22. The insecticidal cowposition of claim 21 wherein A is phenyl or phenyl substituted with one or two substituents each tndepaendently selactead from the group consisting of 4-halo, 4-(Cy- Ca)alkyl, 2,3-di(Cy~Ch)alkyl and 2,6-dihalo; and A’ ie phenyl substituted with one ot two substituents each independently selected from the group consisting of 2-halu, 2,4-dihalo and 3,6- di(y-Cylalkyl; and sgroaomically-acceptable salts theceof .

   23. The insecticidal cowposition of claim 22 wherein A is phenyl substituted with 4d-methyl, 4 - ethyl, 2,6-diflustwy ve 2,3-dimethyl and A’ is phenyl subgbituted with 2-chloro, 2,4-dlchlora, 2- ng bs BAD ORIGINAL P),

   e119 26417 chloro-4-fluorca, 3-mathyl or 3,5-dimethyl; and agronomically~acceptable salts thereof. 24, The insecticidal composition of claim 23 wherein the compound is, 1-(3,b~dimethylbenzayl )-2- : 5 (4-ethylbenzayl)-1-tert-butylhydrazine.

   2b. The insecticidal composition of claim 23 ; wherein the compound is 1-(3-methylbenzoyl)-2-(2,3~ i dinethylbenzoyl)-1-tert-butylhydrazine.

   26. The insecticidal composition of claim 23 wherein the compound is 1-(3,6~dimethyibenzoyl) } -2-(d-mathylbaenzoyl)-l-tert-butylhydrazine.

   27. The insecticidal composition of claim 23 wharein the compound is 1-(2~chloro-4- fluorobenzoy) )-2-benzoyl-1-tert-butylhydrazine. 16 28. The insecticidal composition of claim 23 wherein the compound is 1~(2,4~-dichlora- benzoyl)-2-(2,6-difluorobenzoyl)-1-tert-butyl - hydrazine." \aao ORIGINAL d