Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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
N-R5
HC = QH - C - Ql = CH ~
R3 3
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
-- 6 --
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.
' , ' -'
` ' " '
'.
' 20
,
:
.. , ' '
.
I 30
-- 8 --
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-- 12 --
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-- 17 --
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- 1 9 ~
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.
'
1 30
.
- 20 -
- , ~ , . ~ , . ,
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
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);~
- 22 -
~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~
C H 3
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
:
;~
.'' '
' ~
1, , . ~
- 23 - :
g~
~ .
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O ~) 3 0 O ~ ~ .
0 rl tH t~ d ~ ta 0
~ Q~ ~ ~ ~ ~ .
~ :~ 5.Y O ~1) 3 ~ ~ O- 0 t~
a~ ~ G) ~1 ~ 3 0 O ~ a~ .Y
P:; ~ 3 O ~ ~ --1 d
a) . .
O U~ ~ . ~ ~ tU 4~ 4J
al 1~ '~1 ~ ~ ~ o G rd O
O ~In-r~ ~ ~ ~ 0
0
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. . : `
. ~,(d . .
t ~ ~ ' . .
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.' ' ~ " ~ .. ~ . : . .
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.
-- 24 --
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s ~" n~ Y i~ ~i
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~9~$
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:
, ;~
.
- 3
.
- 27 -
1053B9~1S
o ~ o ,,1 0
o o
1 ~ ~, O O o
. . ~ ~ ::
. . ,, 3;
~' . ' , ~ ~ Z :~
~ ~ ! ,.3 ~ ~
.. . ..
I ~,
-28-
. - .. .. - ,
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.
.
''`~
,
':
..
.
~ 29 -
.. ....
., , ~ -: .: : . .
9~i
~ .
a
U~
a) o O o
. .~ ~ ~ ~ ~ ,,
. U~
o
U~ ~ .
.
~ ~ ~ I o~
~ o C~
- . .
. . ,
.:
. .
. - .
,~ .
~ 8, o o o ~
~ ~: o ~ ,~ .
. . :: . ~ .
~: . ;~;,
:.
.
.. .
U~ e~ ~
: . . . ~;
- . .
- . : , .
:~ ~ 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
- 31 -
~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 ~
:
:
- 32 -
.
l . .,~
c E _ _ I ` ::
Q) o O o
1. .LI' 1~ - .
O o E~ o
O o ~ o : .
~lo ~ _ _~
~: h o E o o . ~:
o o~ o
rl
D~ u~ O E
. O c: IJ h _
~¦ ~J h O :1 E o
1~ . O ~ o o
~) E~ ~ ~ :`
!l ~" _ o E o , ~. .
I u ~1 O ~ ' `~' ' ' '
:~ o o . ,,,~
l ~ o~ o
~1~ i ~ 1~ ~ ~ ~
. E __ _ _ . _ . ~ . :
. , ' ~ : l
. E~ ~'0
~ O ~
: c ~ ~a h-".
l . '' ' ~1~ ~ ~
. ~
. ~ ~--~ O .
,. , ~, O v~ : ;
I . U'l ~ o ~ ~
. . _ , ,.
. ` '~
1.
. ":
- 33 - ~
.
....... .. ...
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.
1 30
_ 34 _
