CA1098905A - Pentadienone hydrazones as insecticides - Google Patents

Abstract

ABSTRACT OF THE INVENTION

A method for controlling insects by contacting the insects, and/or applying to their habitat or food supply, with an insecticidally effective amount of a compound of the formula:

Description

me invention relates to a method for controlling insects, particularly Lepido~terous insects, Orthipterous insects, Dipterous insects and Hymenopterous insects by contacting the insects with, and/or applying to their habitat or food supply, an insectic.idally effective amount of a pentadienone hydrazone having the structure:

DN-R
N~l-C

HC = QH - C - Ql = CH ~

wherein Rl and R2 each represents hydrogen, halogen, CF3, Cl~C4 alkYlr Cl-C3 alkoxy or Cl-C4 aIkylthio; R3 is hydrogen or methyl, provided that when R3 is methyl, Rl and R2 are also methyl; R4 and R5 represent hydrogen or Cl-C4 alkyl, and when taken together, an alkylene group of 2 to 6 carbon atoms, a methyl, dlmethyl, or phenyl alkylene group of 2 to 4 carbon atoms; and R6 is hydrogen or Cl-C4 alkyl; or salts thereof.
The invention also relates to the novel compound 1,5-bis(~ -trifloro-_-tolyl)-1,4-pentadiene-3-one ~1,4,5, 6-tetrahydro-5,5-dimethyl-2-pyrimidinyl) hydrazone.

The invention also relates to a method for pro-tecting agronomic crops, trees, shrubs, ornamentals, and , ^, 1 .~
:,''~

~L 1398~5 the like, from attack by insects, by applying to the crops an insecticidally effective amount of a compound having the above structure.
Pentadien-3-one substituted amido hydrazones are described in United States Patent No. 3,878,201 (1975) as anti-malarial and anti-tubercular agents for warmrblooded animals.
Preferred cGmpounds for use as insecticidal agents and as protecting agents for crops have the above structuret wherein R1 and ~ represent the same substituent and the substituent is H, Cl, Br, CF3, Cl-C3 aLkyl, methoxy or me-thylthio; R3 is hydrogen; R4 and R5 each represent hydro-gen, Cl-C3 alkyl, C2-C6 alkylene, or methyl, dimethyl, or phenyl C2-C4 alkylene; R6 is hydrogen; and the acid addition salts thereof, preferably the hydrochloride, hydrobromide or hydroiodide.
- Still more preferred are compounds as described above, wherein ~ and R2 are each ~-chloro or each p-CF3;
R3 a~d R6 are each hydrogen; and R4 and R5 are taken together and are C2-C6 alkylene or methyl, dimethyl or phenyl C2-C4 alkylene; R6 is hydrogen; and the acid addition salts thereof, preferably hydrochloride, hydrobromide or hydroiodide.
In acaordance with this invention, it has been found that control of insects, particularly Lepidopterous insectsr Orthopterous insects, Dipterous insects and Hymenopterous insects and protection of agronomic crops, trees, shrubs and ornamentals, from attack by the insects, can be achieved by the application of an in-secticidally effective amount of a :

- 2 -j, pe~tadienone hydrazone to the crops or to the habitat or food supply of the insects. ~n ~ractice, generally about 0.28 kg/hectare ~11.2 kg/hectare, and preferably 0.56 ~gf hectare to 4.8 kg/hectare of the pentadienone hydrazone is effective or insect control and/or for crop ~rotection.
The hydrazQnes o~ this invention can be applied in either liqui~. or solid form. They may he applied in solid for~ as dusts or dust concentrates, or in liquid for~ as emulsifiable concentrat~s, flowable liquids or wettable powder~ which are dispersed in water or other inexpensive liquid for application as a.finely divided spray.
A typical emulsifiable conce~trate can be prepared by admixing from about 12% to 29% by weight of the pentadie-none hydrazone, about 8% to 12% by weight of a blend of non-ionic emulsifiers such as T-~ulz 339 (sold by Thompson-~ayward of Kansas City, Xansas), or polyoxyethylene deriva-. tives and blends with alkyl aryl sulfonates, and about 59%
to 80% by weight of cyclohexanone or a heavy aromatic solvent having a mixed aniline between 30F. and 95F.~ a specific 20 gravity between 0.880 and l.S at 60/60F., and an aromatic content of 60~ to 100~. These formulations provide rom 119.8 g/liter to 239.6 g/liter of the active hydrazone, and are generally diluted with water for application as a ~ilute liquid. However, said formulations can also be applied in the form of un~iluted discrete droplets as low volume or ultra low volume spray~. For such application, the emulsifi-able con~entrate is usually applied with apparatus designed to disperse the liq~id in the form of finely divided discrete droplets having a mass median diameter of from 25 to lS0 30 microns.

. A typical wettable powder ~ormulation can be pre-pare~ by grinding together about 34~ by weight of a synthetic calcium silicate, 12~ by weigh~ of a ~spersing agent such ~~ * Trademark ` ~5 as sodium lignosulfonate, 4~ by welght of a wetting agent such as an alkyl aryl sulfonate, and 50% by weight of the pentadienone hydrazone. .Such formulation ~s generally dis- ;
persed in water fox application as a liquid spray.
Pentadienone hydrazones, as re-presen~ed by the formula set forth above, are useful ~or the control of insects, especially a wide variety of Lepidopte.rous insects, Orthopterous insects, DipterOus insects and Hymenopterous insects.
' 10 ~he pentadienone hydrazones of this invention are highly effective for controlling insects of the orders Ortho~tera and Di.ptera and especially active and very selective against Lepidopterous larvae such as southern armyworms ~Spodoptera eridania (Cramer)], cabbage loopers 1'5 ~Trichoplusia ni (Hubner)], tobacco budworms lHeliothis virescens (Fabricus)]/ gypsy moth ~Porth tria dispar (L.)], -and the like, at 10 to 1000 ppm rates~ they do not appear '.
, - to be especially toxic to most beneficial insects r and thus are useful.for pest management and integrated control.pro- . :
grams~ Additionally, I have found that the above-identified compoun~s exhibit relatively low mammalian toxicity when ,ingested, and are only sligh~ly irritating when introduced directly into the eye of a rabbit. Moreover, these compounds .. show virtually no phytotoxicity to plants at rates of applica-tion up to 11.2 kg/hectare..
Advantageously, the pentadien-3-one hydrazone compounds of this invention are active as stomach poi~ons thus are effective against insects with'chewing mouth parts as well as those with sponge and lapping mouth parts. They are especially effective for the control of an s, Family Formicidae, and may be used for the control of fire ants such as the southern fire ant, Solenop3is x ~ ~ (xyloni,) leaf-cutting ants AcRoMy~MFx versicolor (Pergande)~
~ 4 -Argentine ants IRIDOMYREMEX humilis (Mayr)~ black carpenter ants, CAMPONOTUS p nnsylvanica (DeGeer~, cornfield ants LASIUS alienus (Foerster), pavement ants TETRAMORIUM
caespitum, larger yellow ants ACANTHOMYOPS interjectus (Mayr), thief ants SOLENOPSIS molesta (Say), and the red imported fire ant Solenopsis invicta Bruen, and the black imported ~ire ant, _lenopsis saevissima richteri. These ants are serious economic pests generally ound in the warmer climates such as the subtropical and tropical æones. They feed on seeds and tender stems of young plants and are responsible, annually, for substantial damage to agronomic crops. They have likewise been known to attack humans, nestin~ birds, livestock, poultry and household pets. As such, it ls most desirable to control these economic pests.
- 15 Control of these pests can be achieved with treated baits that are distributed in ~he crop area, pasture, park or other location in which ant control is desired, and made available to worker ants. The workexs carry the treated bait to the colony where it is consumed by the queens and ~0 the youn~ antsl thus leadin~ to their destruction.
~ aits can be prepared, for example, by admixing the pentadienone hydrazone with peanut butter, citrus pulp, ap~le ~umice, wheat-bran, corn meal-sugart and vegetable oils such as soybean oil and dis~ributed as is: or these compositions can be placed in soda ~traws on carriers such as corn cob grits, clays, pumice, synthetic polymer compo-sitions or the like and distributed in the area of the colony. Use of these baits ha~ particular advantage, since such method of distribution poses little or no hazard to animals that may ~requent the crop area.
The following example~ illu8trate the in~ention~
. ~

- 5 - ~

~XAMPI,E 1 The insecticidal activity of the compounds of this invention is demonstrated by the following tests, wherein pentadienone hydrazones are evaluated against ~est insect species at rates of ~rom 10 to 1000 ppm. Test ~ormulations and procedures used for evalua~ion are as follows:
Test Formulations.
A. 100 mg of the test material is weighed7 placed in a ~unnel over a 113 g narrow-mouth bottle~ and rinsed into the bottle with a 35 ml scoop of acetone, followed by a ~coop o water and another scoop o~ acetone to yield 1000 ppm in 65~ acetone. If the material is not soluble, it is broken up with a glass rod~ and used as a suspension.
- 15 B. This stock solution ("A") is used to make 300 ppm 501u-tions or suspensions by pipetting 30 ml of "A" into a bottle containing 70 ml of 50% acetone to yield 300 ppm.
Further dilutions in 50% acetone are made as required.
C. Tests requiring 10 ppm acetone solutions: 1 ml of 'IA'' is pipetted into 99 ml of acetone to yield 10 ~pm.
Additional dilutlons are made using 50~ acetone as required.
Initial Tests .
Tobacco Budworm - ~eliothls virescens (Fabricus).
.. , ~ .
A cotton plant with 2 true leaves expanded lS dip-ped for 3 seconds with agitation in 300 ppm solution.
1.27 to 1~91 cm square of cheesecloth with about 50 to 100 budworm eggs 0-24 hours old is also dipped in the test solu-- tion and placed on a lea of the cotton plant, all being placed in the hood to dry. The leaf with the treated bud-worm eg~s is removed from the plant and placed in a ~26 g Dixie cup with a ~et 5 cm piece of dental wick and covered with a lid. ~he other leaf is placed in a similar cup with a wick and a piece of cheesecloth infested with 50-100 newly hatched larvae is added before covering the cup with a lid. After 3 days at 80F., 50~ r.h., observations of egg hatch are made, as well as kill of newly hatched larvae~
any inhibition of feeding, or interference o~ any sort with normal development.
Southern Armyw~rm - Spodol~_era eridania (Cramer).
':
A Sieva lima bean plant with just the primary leaves expanded to 1.91 cm is dipped for 3 seconds with agitation in the "A" solution o 1000 ppm and set in the hood to dry. Following this, one leaf is placed in a 9 cm petri dish which has a moist ilter paper in the bottom and 10 third-instar armyworm larvae about 1 cm long. This dish is covered and held at 80F., and 50% r.h. After 2 days, mortality counts and estimates of the amount of eeding , are made. Compounds showing partial kill and/or inhibition - of feeding are held for an extra day for further observa-tions. Those materials which produce greater than 75%
- mortality, or which show only trace feeding damage are further tested~
All compounds showing activity as defined above are retested, using the second leaf on the bean plant, after an interval of 7 days from original treatment, as an assay of residual activity.
Seaonc~ar~ Tests.
Tobacco Budworm - Heliothis virescens ~Fabricus~
Third Instar.
Three cotton plants with just expanded cotyledons are dipped in 1000 ppm ~olution and placed in the hood to dry. When dry, each cotyledon ~ cut in halfl and 10 are aach placed in a 28 ~ plastic medicine cup conkaining a 1.25 cm dental wick ~aturated with water and one third-instar budworm larva is added. The cup is capped and hel~

~S

for 3 days at 80F 50~ x.h., after which morality counts are made~ Compounds killing more than 75% of the larvae are further tested.
Cabbage Looper - Tr'ichoplusia'nl (Hubner) - Third Instar.
A true leaf of a cotton plant is dipped into the test ~olution, agitated for 3 seconds, and removad to dry in an exhaust hood. ~en dry, ~he leaf is pIaced in a 9. O
'cm petri dish with moist filter paper on the bottom. Ten third-instar larvae are added the lid placed on the di~h.
10' Mortality counts are made after 3 days at 80F and 50 ~ 10%
,` r.h. Compoun~s killing more than 75% of the loopers are further tested.
' Data obtained are reported in Table I below.

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Red imported Fire ant~ Sol~nopsis in~icta (Buren) _ Red imported fire ants ( ~ invic-ta Buren) obtained out-of-doors under natural conditions were used in the imported fire ant screen. Approximately 0.5 cu. fto of an active ant mound was placed in a plastic tub (13" x 13"
x 8") and aged in the laboratory for 3 days before use.
The top 3 inches on the inside of the tub were dusted with talc to prevent the ant3 from escaping. Water was added to the mounds as needed both before and after treatment to help ~ceep them frOm becoming too dry. The compounds were dispersed in soybean oil starting at a low concentration of approximately 0~05%. The concentration was increased a~
various increments to approximately 1.0%. Low concentra-tions were used first to determine if the compound was - 15 palatable to the ants. Approximately 7.5 grams of soybean oil containing the toxicant were poured over a small wad of absorbent cotton in a 3-oz. Dixie~ cup. The side of the , Dixie cup was placed on to~ of the mound. Usua1ly 3 tubs - 'were used per concentration. rlortality counts and/or ratlngs were made at 6 weeks after treatment or longer is ` warranted. The te,~mperature of the holding rooms was approxi-ma~ely 26C. with a relative humidity of approximately 50%.
Data obtained are reported in Table II below.

' .

- , ~ , . ~ , . , 89~5 TA~LE II
ST~UC~URES AND NAMES
Pentadiene-3-one~, 1,5-bis(a,a,a-trifluoro~p-tolyl)~
(1,4,5,6-Tetrahydro-5,5-dimethyl-2 pyrimidinyl)hydrazone F3C ~ -CH=CH-C~CH=C~ ~ C~3 _NH4a~_~CH3 H
1,4-Pentadien-3-one, 1,5-bis~-chlorophenyl)-, t3a~4~ 6~7~7a-hexah~dro-2-benzimidazolyl)hydrazone~ ~
Isomer ~ :

Cl~CH5~CHC CH=C8~Cl ~ ~''I :
.

1,4-Pentadien-3-one, 1,5-bis(~-chlorophenyll-, (1j4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone - ~

C1 ~ CH Cli-C-CII~CH ~ Cl ~H ~ H

1,4-Pentadien-3-one, 1,5~bis~a,~a-trifluoro-~-to1yl)-, . .
(E,E) , azine with hexahydro-2~-1,3-diazepin-2-one F3C ~ IIH il ~ CF3 . HC~~- H
#(NJ

~ 21 -9~gS

TABL~ II (Cont'd) ! . STRUCTU~ES AND NAMES
1,4-Pentadien-3-one, 1,5-bis(~-chlorophenyl~-, ~1,4,5,6-tetrahydro-5,5-dimethyl-2~yrimidinyl)hydrazone hydrochloride, compound. with ethanol ;Cl- ~ CH~CH-~-CHSCH ~ ~ ~1 . IJ~l . C2H5-OH
-NH~ kH3 . C~3 1,4-Pentadien~3-one, l,S~bis(p-chlorophenyl)-, (3a,4,5,6,7,7a-hexahydro~2-benzimidazolyl)hydrazone, hydrochloride CA

Cl- ~ -CH-CHC-CH=CH ~ Cl N-N}I ~ . HCl ........ .. . ...... ...... .. .. . ... .
-- - :
~ Pentadien-3-one, 1,5-bis( a,a,a-trif luoro-~-tolyl~
.
(E,E)-, azine with hexahydro-2H-1,3-dlazepin-2-one-, hydrochlor id~

HC ~ RCl H` -Guanidine, 1- (1P-Ch1OrO-~- (p-chlorostyryl)cinnamylidene]-amino)-2,3-diisopropyl-, hydriodide -C1 ~ - CH~CHCCII~CH ~ Cl HI ~
'. - 11 1 .
N-N~ -NH-CH(C~3)~
N-CH(CH3);~

~A~LE II (Cont'd) ~TRUCTURES AND NAMES
._ 1,4-Pentadien-3-one, 1,5-bis(p-chloxophenyl)~, 5-methyl.-2-imidazolin-2-ylhydra zone, hydrochloride Cl ~ CH~CII-C-CI~CH 4~ Cl ~ HCl N--N-NH4~

1,4-Pentadien-3-one r 1,5-bis~p-chlorophenyl)-, ~4-phenyl-2-imidazolin-2~yl)-hydrazone CA

(`'1 ~3 CH~ CH(,iCH~CII ~3 Cl tl-NH ~3 :

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E~IPLE~
The insecticidal activity of the compounds of this invention is.further demonstra~ed by the ~ollowing tests, wherein pentadienone hydrazones are evaluated as stomach S poisons against test insect specie~ at rates of from 30 to 1000 ppm. Test formulations and evaluation procedures are as follows:
Test I German cockroaches (Blat~ella ~ermanica (Linnaeu5)).
A. 11.0 mg of 1,5-bis(a,a,a-trlfluoro-~-tolyl)-1,4-I0 pentadien-3 one~ 4,5,6,7-~etrahydxo~ 1,3-diazepin-2-yl - hydrazone were placed in 11.0 g of creamy peanut butter and . thoroughly mixed. This is equivalent to a concentrativn of . approximatelyØ1% or 1000 pm.
B. 1.0 g of A was added to 9.0 g of peanut butter lS and thoroughly mixed. ~his is equivalent of 0.01% or 100 ppm.
C. 5.0 g of peanut butter served as the control.
~pproximately S.0 g of bait were placed in a 3 cm x 1 cm high plastic cup. The plastic cup of bait and a water wick were placed in a cage 8 inches in diameter and 2.5 inches high.
: 20 The bottom of ~he cage was an eight-inch diameter plate of glass resting on a half inch rim which extended inward from .the stainless steel side. Twenty adult male German cockroaches were placed in each cage. The cage was covered with a 16-mesh :
.. copper wire screen lid. The cages were held at approximately 27C~
Results are in the following table:

, ;~

.

.

1053B9~1S

o ~ o ,,1 0 o o 1 ~ ~, O O o . . ~ ~ ::
. . ,, 3;

~' . ' , ~ ~ Z :~

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.. . ..
I ~, . - .. .. - , Test II. ~louse flies (Musca domestica Linnaeus~
l. 400 g of sugar and 400 g of powdered milk were thorou~hly mixed in a gallon ice cream carton.
A. 222.2 mg of 1,5 bis(a,a,~-trifluoro-p-)-1,4-pentadien-3-one, 4,5~6,7-tetrahydro-lH-1,3-diazepin-2-yl-hydrazone 90~ pure were added to ~no.n g of ~l and thoroughly ~ixed. This is equivalent to a concentration o~ 0.1% or lO00 ppm.
B. 30.0 g of A were added to 70 g of Xl and mixed well. Concentration = 0.03~ or 300 ppm.
C. lO.0 g of A were added to 90 g of ~1 and mixed well. Concentration - 0.01~ or 100 ppm.
D. 3.0 g of A were added to 97 g of #1 and mixed well. Concentration = 0.003% or 30% ppm.
~. Control was #1 only.
Fifty grams of dry bait in a 9.0 cm petri dish bottom were :~ .
placed in each house fly cage. ~ach~cage~ 12" x 12" x 12"
`::
was made of~ 16-mesh copper wire ~creen supported by a wooden ~frame. One hundred house~fly pupae and a water wick were placed in each cage. The cages were held at 28+?.C. Th~
flies emerged in 2-3 days. Results are in the following table.

.
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..

.

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:~ ~ 30 EXAMPLE III
I The insecticidal ~ctiv~ty of the compounds of f this invention is demonstrated by the following tests, wherein pentadienone hydrazones are evaluated against test insect species at rates o~ from 10 to 1000 ppm, ~Test formulations and procedures used for evaluation are as follow3: :
Test Formula~ions t' A. 100 Milligrams of the test material is weighed, placed in a funnel over a 113 g naxrow-mouth bottle, and rinsed j 10 into the bottle with a 35 ml scoop of acetone, followed by a scoop of water and another scoop of acetone to yield 1000 ppm in 65% acetone. If the material is not soluble, it is broken up with a glass rod and used as a ~ suspension.
! 15 B. This stock solution ~"A") is used to make 300 ppm ~ solutions or suspensions by pipetting 30 ml of "A" into . .
a bottle containing 70 ml of 50% acetone to yield iO0 ppm.
` ~ Further dilu~ions in 50~ acetone are made as required.
C. Tests requiring 10 ppm acetone solutions: 1 ml of "A"
is pipetted into 9g ml of acetone to yield 10 ppm.
Additional dilutions are made usinq 50~ acetone as required.
Initial TestS
; .
Tobacco Budworm - [Heliothis virescens (Fabricus)].
.~
. ~
A cotton plant with two true leaves expanded is dipped for 3 seconds with agi~ation in 300 ppm solu~ion. A
1.27 cm to 1.91 cm square of cheesecloth with about 50 to 100 budworm eggs 0-24 hours old is also dipped in the te~t solu-tion and placed on a lea of the cotton plant, all being ¦ 30l placed in the hood to dry. The leaf with the treated budworm eggs is removed from the plant and placed in a 226 g DixiP
cup with a wet 5 cm piece of dental wick and covered with a i ~1989~5 ~ lid. The other leaf i5 placed in ~ simil~r cup with a wick j ' and a piece of cheesecloth infested with 50-100 newly hatched larvae is added before covering the cup with a lid.
After 3 days at 80F, 50% r.h., ob6ervations of e~g hatch are made, as well as kill of newly hatched larvae, any inhibition of feeding, or interference of any sort with normal development.
Secondary Tests Tobacco Budworm - [Heliothis virenscens ~Fabricus)~ - Third Instar Three cotton plants with just expanded cotyledons are dipped in 1000 ppm solution and placed in the hood to dry. When dry, each cotyledon is out in half, and 10 are each placed in a 28 g plastic medicine cup containing a 1,25 cm dental wick saturated with water and one third-instar budworm larva is added. T~e cup is capped and held for 3 days at 80'F, 50% r.h., after whlch mortality count are made~ Compounds killing more than 75% of the larvae are further tested.
Cabbage Looper - ~Trichoplusia nl (H~bner)] - Third Instar . ~
A true leaf of a cotton pla~t is dipped into the ~test solution, agitated for 3 seconds, and removed to dry . . ..
in an exhaust hood~ When dry, the leaf is placed in a 9.0 cm petri dish with moist filter paper on the bottom. Ten third instar larvae are added and the lid placed on the dish.

Mortality counts are made after 3 days at 80F and 50 +

10% r.h. Compounds killing more than 75~ of the loopers I ~ are further tested.

, Data obtained are reported in the Table below.
! 301 ~
:
:

.

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....... .. ...

EXAMPLE IV
~ . , diene-3-one '(1,4','5,6-t'etr'ahydro-5,5-dimethyl-2-pyri~idinyl)-hydrazone.
CH ~ ~ t ~ CF~2 To a mixture of 2.1 g of 5,5-dimethyl--1,4,5,6-tetra hydropyridinium-2-ylhydrazine hydroiodide and 3.2 g of 1,5-bis(~,~,a-trifluoro-p-tolyl)-1,4~-pentadiene-3-one in 6 ml of absolu~e e~hanol was added one drop of 47% hydriodic acid.
The mixture was heated at reflux or 2 to 3 hours and then cooled in ice. The yellow hydroiodide salt which precipitated was collected by filtration and washed with ethanol. The - lS hydroiodide salt was neutralized by stirring with 15 ml of ethyl acetate and 15 ml of saturated sodium carbonate solution.
The ethyl acetate mixture was separated rom the a~ueous phase, dried over magnesium sulfate, and concentrated to give a red oil. The oil was mixed with a litt7e ether, and the mixture refrigerated. The resulting solids were collected and washed with ether and amounted to 1.2 g, melting point 163.5-16~.5C. Analysis calculated or C25H24F6M~: C, 60.72;
H, 4.89; N, 11.33. Found: C, 60.54; ~, 4.73; N, 10.43. Ths product exists in different crystalline forms, and when re-crystallized from isopropyl alcohol, has a melting ~oint o189-191C.

_ 34 _

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula:

2. A method for controlling insects comprising, contacting the insect, their habitat, and/or their food supply, with an insecticidally effective amount of a compound having the structure:

wherein R1 and R2 each represent hydrogen, halogen, CF3, C1-C4 alkyl, C1-C3 alkoxy or C1-C4 alkylthio; R3 is hydrogen or methyl, provided that when R3 is methyl, R1 and R2 are also methyl; R4 and R5 represent hydrogen or C1-C4 alkyl, and when taken together, an alkylene group of 2 to 6 carbon atoms, a methyl or a phenyl alkylene group of 2 to 4 carbon atoms, or a dimethyl alkylene group of 2 to 4 carbon atoms, and R6 is hydrogen or C1-C4 alkyl; or salts thereof.

3. The method according to Claim 2, wherein R1 and R2 are each p-chloro or p-CF3; R3 and R6 are each hydrogen; and R4 and R5 taken together are C2-C6 alkylene.

4. The method according to Claim 2, wherein the insects are Lipidopterous, Orthopterous, Dipterous or Hymenopterous insects, and the compound is applied at the rate of from 0.28 kg/hectare to 11.2 kg/hectare.

5. The method according to Claim 2, wherein the compound is l,5-bis(a,a,a-trifluoro-p-tolyl)-1,4-pentadien-3-one (l,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl) hydrazone.

6. The method according to Claim 2, wherein the compound is 1,5-bis(a,a,a-trifluoro-p-tolyl)-1,4-pentadien-3-one 4,5,6,7-tetrahydro-lH-1,3-diazepin-2-yl-hydrazone.

7. The method according to Claim 2, wherein the compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one 4-phenyl-2-imidazolin-2-ylhydrazine.

8. The method according to Claim 2, wherein the compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one 4,5, 6,7-tetrahydro-1H-1,3-diazepin-2-ylhydrazone.

9. The method according to C1aim 2, wherein the compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one 3a,4,5,6,7a-hexahydrobenzimidazol-2-ylhydrazone.

10. The method according to Claim 2, wherein the compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one 1,4, 5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazone.

11. The method according to Claim 2, wherein the compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one/4, 4-dimethyl-2-imidazolin-2-ylhydrazone or the acid addition salt thereof.

12. A method for protecting agronomic crops, trees, shrubs and ornamentals, from attack by insects comprising, applying to the crops an insecticidally effective amound of a compound of Claim 1.