Pentadienone hydrazones, method for preparing the same, and insecticidal use thereof

There are provided insecticidal pentadienone hydrazones and methods of preparation thereof. There is further provided a method for using the aforesaid compounds for the control of insects, especially Lepidopterous insects, and for the control of ants, Family Formicidae, especially fire ants.

The present invention relates to novel insecticidal pentadienone 
hydrazones. More particularly, it relates to pentadienone hydrazones of 
the structure represented by formula: 
##STR1## 
wherein R.sub.1 and R.sub.2 are each selected from Y--CF.sub.2 X--, 
hydrogen or halo, provided that at least one but not both of R.sub.1 and 
R.sub.2 is Y--CF.sub.2 X--; Y is selected from hydrogen, fluorine, 
--CHF.sub.2 or --CHCl.sub.2 ; X is oxygen or sulfur; R.sub.3 and R.sub.4 
each are alkyl (C.sub.1 -C.sub.4) and, when taken together they form an 
alkylene group of 2 to 4 carbon atoms or a methyl or a 
dimethyl-substituted alkylene group of 2 to 4 carbon atoms, and the 
inorganic acid addition salts thereof. 
A preferred group of compounds represented by hereinabove defined structure 
are those wherein R.sub.1 is selected from CHF.sub.2 O--, CHF.sub.2 S--, 
CF.sub.3 O--, CF.sub.3 S-- or CHF.sub.2 --CF.sub.2 O--; R.sub.2 is 
hydrogen; and R.sub.3 and R.sub.4 taken together with the amidino group 
##STR2## 
they are attached to represent the moieties 
##STR3## 
and the acid addition salts thereof, preferably the hydrochloride, 
hydrobromide or hydriodide. 
Among the compounds of the invention which can be prepared in accordance 
with the invention are illustratively: 
1,5-bis[p-(trifluoromethylthio)phenyl]-1,4-pentadien-3-one 
(4-methyl-2-imidazolin-2-yl)hydrazone; 
1,5-bis[p-(trifluoromethylthio)phenyl]-1,4-pentadien-3-one 
(1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone; 
1,5-bis[p-(trifluoromethoxy)phenyl]-1,4-pentadien-3-one 
(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)hydrazone; 
1,5-bis[m-(difluoromethoxy)phenyl]-1,4-pentadien-3-one 
(1,4,5,6-tetrahydro-2-pyrimidinyl)-hydrazone; 
1,5-bis[p-(1,1,2,2-tetrafluoroethoxy)phenyl]-1,4-pentadien-3-one 
(1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone; 
1,5-bis{p-[(difluoromethyl)thio]phenyl}-1,4-pentadien-3-one 
(1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone; and 
1,5-bis[p-(difluoromethoxy)phenyl]-1,4-pentadien-3-one 
(1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone; and acid 
addition salts thereof, preferably the hydrochloride, hydrobromide or 
hydriodide. 
Advantageously, the compounds of the invention find utility in controlling 
insects, particularly Lepidopterous insects, and ants, Family Formicidae, 
by contacting the insects with, and/or applying to their habitat or food 
supply, an insecticidally effective amount of a pentadienone hydrazone of 
the structure: 
##STR4## 
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as hereinabove defined; 
and salts thereof. Further, the invention finds utility in protecting 
agronomic crops, trees, shrubs, ornamentals, and the like from attack by 
insects, by applying to the crops an insecticidally effective amount of a 
compound having the above-identified structure. 
It is unexpectedly found that the insecticidal pentadienone hydrazones of 
the present invention can be conveniently prepared by a reaction sequence 
graphically illustrated and described as follows: 
##STR5## 
wherein each of the R groups are as hereinabove defined and HX represents 
a mono or divalent inorganic acid, such as hydrochloric, hydrobromic or 
hydriodic acid. In the above sequence, the desired product (I) is shown as 
the HX salt. The corresponding pentadienone hydrazone free base may be 
obtained by treating the HX salt with an aqueous solution of a base, such 
as sodium or potassium bicarbonate, sodium or potassium carbonate, sodium 
or potassium hydroxide or ammonium hydroxide. 
As above illustrated, two moles of a substituted benzaldehyde (II) are 
reacted with one mole of acetone in an aqueous alcohol in the presence of 
an alkali metal base such as sodium or potassium hydroxide at a 
temperature range of 10.degree. to 40.degree. C., preferably 20.degree. to 
25.degree. C. for a period of time from one to three hours, or until the 
condensation reaction is essentially complete to yield the corresponding 
pentadienone (III). Next, the so-obtained pentadienone is condensed with 
an equimolar (or, if desired, slight excess) amount of a salt of the 
appropriate hydrazine (IV) in an alcohol at 50.degree. C. to 80.degree. C. 
or at the boiling point of said alcohol for a period of time of one to 
five hours or until the condensation reaction is essentially complete to 
yield the salt of a pentadienone hydrazone (I). Exemplary of the alcohols 
used in the above reaction sequences are methanol, ethanol, isopropanol, 
and mixtures thereof. The pentadienone hydrazone may be recovered from the 
above salt, if desired, by treating said salt with a dilute aqueous 
solution of an inorganic base, such as sodium or potassium bicarbonate, 
sodium or potassium carbonate, sodium or potassium hydroxide, or ammonium 
hydroxide. 
In accordance with this invention, it is found that both control of 
insects, particularly Lepidopterous insects, and protection of agronomic 
crops, trees, shrubs and ornamentals from attack by the insects, can be 
achieved by the application of an insecticidally effective amount of a 
pentadienone hydrazone to the crops or to the habitat of the insects. In 
practice, from about 0.14 kg/hectare to 11.2 kg/hectare, and preferably 
0.56 kg/hectare to 4.48 kg/hectare of the pentadienone hydrazone is 
effective for insect control and/or for crop protection. 
The desired pentadienone hydrazones can be applied in either liquid or 
solid form. For instance, they may be applied in solid form as dusts or 
dust concentrates, or in liquid form as emulsifiable concentrates, 
flowable liquids or wettable powders which are dispersed in water or other 
inexpensive liquid for application as a finely divided spray. 
A typical emulsifiable concentrate can be prepared by admixing from about 
12% to 29% by weight of a pentadienone hydrazone, about 8% to 12% by 
weight of a blend of nonionic emulsifiers, such as T-Mulz 339 (sold by 
Thompson-Hayward of Kansas City, Kansas), or polyoxyethylene derivatives 
and blends with alkyl aryl sulfonates, and about 59% to 80% by weight of 
cyclohexanone or a heavy aromatic solvent having a mixed aniline point 
between -1.degree. C. and 35.0.degree. C. (30.degree. F. and 95.degree. 
F.), a specific gravity between 0.880 and 1.5 at 15.5.degree./15.5.degree. 
C. (60.degree./60.degree. F.), and an aromatic content of 60% to 100%. 
These formulations provide from 119.8 g/liter to 239.6 g/liter of the 
active hydrazone, and are generally diluted with water for application as 
a dilute liquid. However, said formulations can also be applied in the 
form of undiluted discrete droplets as low volume or ultra-low volume 
sprays. For such application, the emulsifiable concentrate is usually 
applied with apparatus designed to disperse the liquid in the form of 
finely divided discrete droplets having a mass median diameter of from 25 
to 150 microns. 
A typical wettable powder formulation can be prepared by grinding together 
about 34% by weight of a synthetic calcium silicate, 12% by weight of a 
dispersing agent such as sodium lignosulfonate, 4% by weight of a wetting 
agent such as an alkyl aryl sulfonate, and 50% by weight of the 
pentadienone hydrazone. Such formulation is generally dispersed in water 
for application as a liquid spray. 
In general, the pentadienone hydrazones of this invention are especially 
active and quite selective against Lepidopterous larvae such as southern 
armyworms [Spodoptera eridania (Cramer)], cabbage loopers [Trichoplusia ni 
(Hubner)], tobacco budworms [Heliothis virescens (Fabricius)], and the 
like, at 10 to 1000 ppm rates. They do not appear to be especially toxic 
to most beneficial insects and thus are useful for pest management and 
integrated control programs. Moreover, these compounds show virtually no 
phytotoxicity to plants at rates of application up to 11.2 kg/hectare. 
Advantageously, the pentadien-3-one hydrazone compounds of the present 
invention are active as stomach poisons. Thus, they are effective against 
insects with chewing mouth parts (Orthopterous insects such as 
cockroaches, grasshoppers, crickets and Isopterous insects, such as 
termites) as well as those with sponge and lapping mouth parts (Dipterous 
insects, such as flies). They are effective for the control of fire ants, 
such as the southern fire ant, Solenopsis xyloni, the black imported fire 
ant, Solenopsis richteri and the red imported fire ant, Solenopsis 
invicta. They are also effective for the control of ants, such as the 
big-headed ant, Pheidole megacephala, and the Argentine ant, Iridomyrmax 
humilis, that are dominant pests in pineapple and sugarcane fields, and 
for the control of many species of ants that are classified under the 
general category of household ants. Ants are serious economic and public 
health pests. Serious problems created by fire ants are stinging of humans 
and livestock, feeding on plants, particularly-on seedlings and on 
germinating seeds, damage to farm machinery that strike ant mounds, loss 
of crops and refusal of workers to enter infested fields to cultivate and 
harvest crops. Ants invade houses, crawl over food, carry bits of food to 
their nests and also cause damage by establishing their nests in the 
woodwork of houses and other wooden buildings. 
Control of these pests can be achieved with treated baits that are 
distributed in or adjacent to the infested area, such as pasture, park 
dwellings or other locations in which ant control is desired, and made 
available to worker ants. The workers carry the treated bait to the colony 
where it is consumed by the queens and the young ants, leading to their 
destruction. 
In practice, generally about 1.25 g/ha to 75.0 g/ha, and preferably 2.5 
g/ha to 37.5 g/ha of the pentadienone hydrazone is effective for fire ant 
control and/or for crop protection from ants and about 0.0625% to 4% by 
weight, and preferably 0.125% to 2.0% by weight of the pentadienone 
hydrazone is effective for the control of house ants and/or other insects 
that are controlled by bait. 
Baits can be prepared, for example, by admixing the pentadienone hydrazone 
with peanut butter or citrus pulp, vegetable oils such as soybean oil, 
animal fats such as lard and tallow, and with or without an organic filler 
such as bran, and/or an attractant such as lecithin. The composition is 
then placed in soda straws or on a carrier such as puffed grain, corncob 
grits and/or starch matrix and distributed in the area of the colony or 
infestation. Use of these baits has particular advantage, since such 
method of distribution poses little or no hazard to non-target organisms 
that may frequent the infested area.

The invention is further illustrated by the examples set forth below. These 
examples are provided only by way of illustration and are not intended to 
be limiting. All parts, unless otherwise noted, are by weight. 
EXAMPLE 1 
Preparation of p-Trifluoromethoxybenzaldehyde. 
To a solution of hexamethylenetetramine (300 g; 2.14 mole) in ethanol (900 
ml) and water (600 ml) a mixture of 
.alpha.-bromo-4-trifluoromethoxytoluene and 
.alpha.,.alpha.-dibromo-4-trifluoromethoxytoluene (300 g; 1.11 mole; 76:24 
mixture) is added. The reaction mixture is stirred and heated at reflux 
for 3 hours under a nitrogen atmosphere, and then stirred overnight at 
room temperature. 
From the above reaction mixture a cloudy liquid (144.5 g) is isolated and 
then distilled under vacuum to afford 122.2 g (58%) of title product, a 
colorless liquid, b.p. 66.degree.-74.degree. C. at 5-7 mm. NMR (in 
CCl.sub.4) [.delta.=6.15 and 6.75 (AB doublets, 4H, J=8 Hz, aromatics) 
8.85 (S, 1H, --CHO)]. IR.1710 cm.sup.-1 (carbonyl stretch). 
The required mixture of .alpha.-bromo- and 
.alpha.,.alpha.-dibromo-4-trifluoromethoxytoluene is obtained through the 
bromination of p-trifluoromethoxytoluene by the method of Example 8. 
EXAMPLE 2 
Preparation of 1,5-Bis[p-(trifluoromethoxy)phenyl]-1,4-pentadien-3-one 
Acetone (8.7 g; 0.15 mole) is added to a solution of 
p-trifluoromethoxybenzaldehyde (57.0 g; 0.30 mole) in methanol (200 ml). 
The solution is cooled to 20.degree. C. and 10% aqueous sodium hydroxide 
(8 ml) is added dropwise in about 5 minutes. The reaction mixture is then 
stirred at room temperature for 1.5 to 2 hours. During this period a 
yellow solid precipitates from the solution. The mixture is chilled 
overnight, filtered and the isolated yellow solid dried to afford 24.8 g 
(41%) of title product, m.p. 121.degree.-123.degree. C. NMR (acetone-d6) 
[.delta.=7.0-8.0 (M, 12H, aromatics and vinyl)]; IR 1590-1650 cm.sup.-1 
(several bands). 
EXAMPLE 3 
Preparation of 
1,5-Bis[p-(trifluoromethoxy)phenyl]-1,4-pentadien-3-one-(1,4,5,6-tetrahydr 
o-5,5-dimethyl-2-pyrimidinyl)hydrazone 
A mixture of 1,5-bis[p-trifluoromethoxy)phenyl]-1,4-pentadien-4-one (4.02 
g; 0.01 mole), (1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazine 
hydroiodide (2.70 g; 0.01 mole) and ethanol (25 ml) is stirred and heated 
at reflux for 3 hours. The ethanol is then stripped from the reaction 
mixture and the residue washed thoroughly with ether. The residue is then 
stirred with ether (100 ml) and saturated sodium carbonate solution (50 
ml). After about 15 minutes the ether layer is separated, dried and 
evaporated. The residual yellow solid is recrystallized from a 
benzene-hexane mixture to afford 2.6 g (50%) of title product, a yellow 
solid, m.p. 170.degree.-172.degree. C. 
Analysis calculated for C.sub.25 H.sub.24 O.sub.2 N.sub.4 F.sub.6 : C 
57.05; H 4.56; N 10.65; Found: C 56.42; H 4.59; N 10.46. 
EXAMPLE 4 
Preparation of 
1,5-Bis[p-(trifluoromethoxy)phenyl]-1,4-pentadien-3-one-4,5,6,7-tetrahydro 
-1H-1,3-diazepin-2-ylhydrazone 
A mixture of 1,5-bis[p-(trifluoromethoxy)phenyl]-1,4-pentadien-3-one (4.0 
g; 0.01 mole), 4,5,6,7-tetrahydro-1H-1,3-diazepine-2-ylhydrazine 
hydroiodide (2.6 g; 0.01 mole) and isopropyl alcohol (25 ml) is heated at 
reflux for 2 to 3 hours. The reaction mixture is then cooled to 
-15.degree. C., and the precipitated material is isolated by filtration 
and washed with ether. The isolated material is mixed with ether and 
saturated sodium carbonate solution and the mixture stirred for about 15 
minutes. The ether layer is then separated, dried, and concentrated to 
afford 3.8 g (75%) of title product, a bright yellow solid, m.p. 
184.5.degree.-185.5.degree. C. 
Analysis calculated for: C.sub.24 H.sub.22 O.sub.2 N.sub.4 F.sub.6 : 
C 56.27; H 4.29; N 10.94; 
Found: C 56.24; H 4.28; N 10.92. 
EXAMPLE 5 
Preparation of 
1,5-Bis[p-(1,1,2,2-tetrafluoroethoxy)phenyl]-1,4-pentadien-3-one 
Aqueous sodium hydroxide (28.1 ml; 10%) is added dropwise, rapidly, to a 
stirred mixture of p-(1,1,2,2-tetrafluoroethoxy)benzaldehyde (11 ml; 0.069 
mole), acetone (2.4 ml; 0.33 mole), absolute alcohol (135 ml) and water 
(14 ml). The reaction mixture exotherms to 30.degree. C. The reaction 
mixture is then cooled, the precipitated material is filtered, washed and 
dried to afford 3.8 g (25%) of title product. 
EXAMPLE 6 
Preparation of 
1,5-Bis[p-(1,1,2,2-tetrafluoroethoxy)phenyl]-1,4-pentadien-3-one-(1,4,5,6- 
tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone, -hydriodide. 
A mixture of 
1,5-bis[p-(1,1,2,2-tetrafluoroethoxy)-phenyl]-1,4-pentadien-4-one (6.3 g; 
0.135 mole), (1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazine 
(3.65 g; 0.135 mole), hydriodic acid (0.5 ml; 51% aqueous) and absolute 
ethanol (25 ml) is stirred and refluxed for 3.5 hours. The reaction 
mixture is then cooled, the resulting precipitate filtered and dried to 
afford 7.1 g (73%) of title product, a bright yellow solid, m.p. 
214.5.degree.-216.5.degree. C. 
Analysis calculated for C.sub.27 H.sub.27 O.sub.2 N.sub.4 F.sub.8 I: C 
45.13; H 3.79; N 7.8; 
Found: C 45.37; H 4.05; N .778. 
EXAMPLE 7 
Preparation of p-Difluoromethylthiotoluene 
A mixture of sodium hydroxide (202 g; 4.91 mole), dioxane (300 ml), water 
(400 ml) and p-thiocresol (70.0 g; 0.55 mole) is stirred, heated to 
55.degree. C. and chlorodifluoromethane (94 g; 1.1 mole) is bubbled 
through the reaction mixture at a rate to maintain the temperature at 
55.degree. C. by the reaction exotherm. Addition time is 4 hours. The 
reaction mixture is then cooled to room temperature, diluted with water 
(500 ml) and extracted three times with ether. The combined ether extracts 
are washed with 5% potassium hydroxide solution, water and then dried over 
sodium sulfate. The ethereal solution is concentrated to afford 134 g of 
clear yellow liquid. Distillation of same affords 78 g (81%) of title 
product, a water white liquid, bp. 87.degree.-89.degree. C. at 16-18 m. 
EXAMPLE 8 
Preparation of .alpha.-Bromo-p-difluoromethylthiotoluene 
A solution of bromine (18.6 ml; 0.3618 mole) in carbon tetrachloride (25 
ml) is added dropwise over two hours to a gently refluxing (.about. 
55.degree. C.) solution of p-difluoromethylthiotoluene (35.0 g; 0.201 
mole) in carbon tetrachloride (120 ml) containing azobisisobutyronitrile 
(0.1 g) while being irradiated with UV light. The reaction mixture is then 
stirred for one additional hour at reflux and is then concentrated to 
afford 62.8 g of a mixture consisting of 73% by weight of .alpha., 
.alpha.-dibromo-p-difluoromethylthiotoluene and 27% by weight of 
.alpha.-bromo-p-difluoromethylthiotoluene (as determined by proton 
magnetic resonance). 
EXAMPLE 9 
Preparation of p-Difluoromethylthiobenzaldehyde 
To a solution of hexamethylenetetramine (31.2 g; 0.22 mole) in ethanol (90 
ml) and water (60 ml) under a nitrogen atmosphere a mixture of 
.alpha.-bromo-p-difluoromethylthiotoluene and 
.alpha.,.alpha.-dibromo-p-difluoromethylthiotoluene (31.3 g; 27:73 mixture 
of Example 8) is added. The reaction mixture is heated at reflux for 2 
hours then stirred at room temperature for 16 hours. It is then diluted 
with water (500 ml) and extracted 3X with ether. The ether layer is washed 
with water, saturated salt solution and dried over magnesium sulfate. The 
ethereal solution is concentrated to afford 15.0 g (80%) of the title 
product, a yellow oil; 90% real by NMR. 
EXAMPLE 10 
Preparation of 1,5-Bis-{p-[(difluoromethyl)thio]phenyl}-1,4-pentadien-3-one 
Acetone (1.1 ml; 0.051 mole) and p-difluoromethylthiobenzaldehyde (6.0 g; 
0.032 mole) are dissolved in a mixture of ethanol (53 ml) and water (5.3 
ml). The solution is stirred, cooled below 25.degree. C., and a solution 
of sodium hydroxide (10 ml of 10%) added dropwise. After the addition is 
completed, the reaction mixture is cooled to 15.degree. C., the 
precipitated solids are filtered, washed and dried to afford 3.5 g of 
title product. The product can be recrystallized from methanol. 
EXAMPLE 11 
1,5-Bis{p-[(difluoromethyl)thio]phenyl}-1,4-pentadien-3-one 
1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone 
A mixture of 1,5-bis{p-[(difluoromethyl)thio]phenyl}-1,4-pentadien-3-one 
(1.3 g; 0.0033 mole), 
(1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazine hydroiodide (0.88 
g; 0.0033 mole), hydriodic acid (0.2 ml; of 51% aqueous) and ethanol (10 
ml) is stirred and heated at reflux for 18 hours, and then chilled in an 
ice bath for one hour. The precipitated solid (2.0 g) is filtered and 
stirred with a mixture of ethyl acetate (10 ml) and saturated sodium 
carbonate solution for 0.5 hour. The ethyl acetate layer is then 
separated, dried over magnesium sulfate and stripped under high vacuum to 
afford 0.85 g of title product, an orange solid, m.p. 
155.degree.-156.degree. C. 
Analysis calculated for C.sub.25 H.sub.25 N.sub.4 F.sub.4 S.sub.2 : 
C 57.45; H 5.02; N 10.72; 
Found: C 56.75; H 5.15; N 10.42. 
EXAMPLE 12 
Preparation of p-Difluoromethoxybenzaldehyde 
Sodium hydroxide (48 g; 1.2 mole) is added to a stirred suspension of 
p-hydroxybenzaldehyde (48.9 g; 0.4 mole) in dioxane (142 ml) and water (87 
ml). The mixture is heated to 70.degree. C. and chlorodifluoromethane (33 
g) added slowly. When this addition is completed, 50% sodium hydroxide 
solution (32 ml) is added to the reaction mixture, followed by the slow 
addition of chlorodifluoromethane (33 g). This recharging is repeated 
three times, and a total of 96 g (2.4 mole) of sodium hydroxide and 133 g 
(1.54 mole) of (1.54 mole) of chlorodifluoromethane is used in the 
reaction. The reaction mixture is cooled down, diluted with water (1500 
ml) and extracted with ether several times. The ether layers are combined, 
washed with 10% sodium hydroxide and then dried over magnesium sulfate. 
Concentration of the ethereal solution yields 39 g (57%) of a yellow oil. 
This oil is purified by chromatography on a silica gel column using a 
mixture of hexane:methylene chloride (1:3), to afford 27 g (39%) of title 
product. 
EXAMPLE 13 
Preparation of 1,5-Bis[p-(difluoromethoxy)phenyl]-1,4-pentadien-3-one 
A mixture of p-difluoromethoxybenzaldehyde (10.7 g; 0.0622 mole), acetone 
(2.2 ml; 0.0296 mole, ethanol (103 ml) and water (10 ml) is added 
dropwise, rapidly, and with stirring to an aqueous sodium hydroxide 
solution (25.5 ml; 10%). The reaction mixture exotherms to 30.degree. C. 
and a precipitate forms. The precipitate is filtered, washed and dried to 
afford 9.0 g (97.2%) of title product. 
EXAMPLE 14 
Preparation of 
1,5-Bis[p-(difluoromethoxy)phenyl]-1,4-pentadien-3-one-(1,4,5,6-tetrahydro 
-5,5-dimethyl-2-pyrimidinyl)hydrazone. 
A mixture of 1,5-bis[p-difluoromethoxy)phenyl]-1,4-pentadien-3-one (4.5 g/ 
0.0123 mole), 1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazine (3.3 
g; 0.123 mole), hydriodic acid (0.5 ml; 51% aqueous) and absolute ethanol 
(25 ml) is heated at reflux for 3 hours. The reaction mixture is then 
cooled down, the precipitate isolated by filtration to afford 5.5 g (72%) 
hydriodide salt of the title product, m.p. 164.degree.-166.degree. C. 
Analysis calculated for C.sub.25 H.sub.29 O.sub.2 N.sub.4 F.sub.4 I: 
C 48.55; H 4.40; N 9.06; 
Found: C 47.70; H 4.36; N 9.06. 
The above salt (6.9 g) is mixed with ethyl acetate (20 ml) and saturated 
sodium carbonate solution (20 ml), and the mixture stirred for one hour. 
The organic phase is then separated, washed with water, dried over 
magnesium sulfate and concentrated to yield 5.4 g (99%) of an orange 
solid. Recrystallization from isopropanol affords 4.0 g (73%) of title 
product, m.p. 152.degree.-154.degree. C. 
Analysis calculated for C.sub.25 H.sub.26 O.sub.2 N.sub.4 F.sub.4 : C 
61.21; H 5.34; N 11.42; Found: C 61.01; H 5.54; N 11.37. 
EXAMPLE 15 
Preparation of 
1,5-Bis[p-(trifluoromethoxy)phenyl]-1,4-pentadien-3-one-(1,4,5,6-tetrahydr 
o-2-pyrimidinyl)hydrazone. 
By the procedure of Example 14, except substituting 
1,4,5,6-tetrahydro-2-pyrimidinylhydrazine hydroiodide for 
1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazine hydroiodide, the 
title compound, a yellow solid, is obtained, m.p. 140.degree.-142.degree. 
C. 
EXAMPLE 16 
Preparation of 1,5-Bis[p-(difluoromethoxy)phenyl]-1,4-pentadien-3-one 
N,N'-diethylamidinohydrazone 
By following the procedure of Example 14, but replacing 
1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazine hydroiodide with 
N,N'-diethylamidinohydrazine hydroiodide affords the title compound, a 
yellow solid, m.p. 97.degree.-99.degree. C. 
EXAMPLE 17 
Preparation of 
1,5-Bis[p-chloro-m-(difluoromethoxy)phenyl]-1,4-pentadien-3-one-(1,4,5,6-t 
etrahydro-2-pyrimidinyl hydrazone 
By the procedures of Examples 7 through 10, and starting with 
2-chloro-5-methylphenol, 
1,5-bis[p-chloro-m-difluoromethoxy)phenyl]-1,4-pentadien-3-one is 
prepared. This pentadienone is then reacted with 
1,4,5,6-tetrahydro-2-pyrimidinylhydrazine hydroiodide by the procedure of 
Example 11 to afford the title compound, a yellow solid, m.p. 
177.degree.-180.degree. C. 
EXAMPLE 18 
Preparation of 
1,5-Bis[p-(2,2-dichloro-1,1-difluoroethoxy)phenyl]-1,4-pentadien-3-one-(1, 
4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone 
p-Cresol is condensed with 1,1-dichloro-2,2-difluoroethylene to yield 
p-2,2-dichloro-1,1-difluoroethoxytoluene. 
The procedures of Examples 8 through 10 are utilized to convert the above 
compound into 1,5-bis[p-(2,2-dichloro-1, 
1-difluoroethoxy)phenyl]-1,4-pentadien-3-one. 
Reaction of this pentadienone with 
1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazine hydroiodide by the 
procedure of Example 11 affords the title product, a yellow solid, m.p. 
177.degree.-180.degree. C. 
Analysis calculated for C.sub.27 H.sub.26 Cl.sub.4 F.sub.4 N.sub.4 O.sub.2 
: C 49.41; H 3.99; N 8.54; Found: C 48.22; H 3.96; N 8.08. 
EXAMPLE 19 
Preparation of 1,5-Bis[p-(difluoromethoxy)phenyl]-1,4-pentadien-3-one 
(4-methyl-2-imidazolin-2-yl)hydrazone. 
By the procedure of Example 14, but substituting 
4-methyl-2-imidazolin-2-ylhydrazine dihydrochloride for 
1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazine hydroiodide, the 
title compound, a bright yellow solid, is obtained. 
EXAMPLE 20 
Preparation of 
1,5-Bis[p-(trifluoromethylthio)phenyl]-1,4-pentadine-3-one-(1,4,5,6-tetrah 
ydro-5,5-dimethyl-2-pyrimidinyl)hydrazone 
By the procedures of Examples 7 through 10, the compound: 
1,5-bis[p-(trifluoromethylthio)phenyl]-1,4-pentadine-3-one is prepared 
from p-trifluoromethylthiotoluene. 
Reaction of this pentadienone with 
1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazine by the procedure of 
Example 11 yields the title product, a yellow solid, m.p. 172.degree. 
C.-174.degree. C. 
EXAMPLE 21 
Preparation of 
1,5-Bis[m-bromo-p-(difluoromethoxy)phenyl]1,4-pentadien-3-one-(1,4,5,6-tet 
rahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone 
By the procedures of Examples 7 through 10, the compound: 
1,5-bis[m-bromo-p-(difluoromethoxy)phenyl]-1,4-pentadien-3-one is prepared 
from 2-bromo-4-methylphenol. 
Reaction of this pentadienone with 
1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinylhydrazine hydroiodide by the 
procedure of Example 11, affords the title product, a dark yellow solid. 
EXAMPLE 22 
Evaluation of the Insecticidal Activity of the Compounds of the Invention 
The activity of the hereinabove compounds of this invention is demonstrated 
by the following tests, wherein pentadienone hydrazones are evaluated 
against test insect species at rates ranging from 10 to 1000 ppm. Test 
formulations and procedures used for evaluation are as follows: 
Test Formulations 
A. 100 Mg of the test material is weighed, placed in a funnel over a 113 g 
narrow-mouth bottle, and rinsed 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. 
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 300 ppm. Further dilutions in 50% acetone are made as 
required. 
C. Tests requiring 10 ppm in acetone solutions: 1 ml of "A" is pipetted 
into 99 ml of acetone to yield 10 ppm. Additional dilutions are made using 
50% acetone as required. 
Initial Tests 
Tobacco Budworm--Heliothis virescens (Fabricius) 
A cotton plant with 2 true leaves expanded is dipped for 3 seconds with 
agitation in 300 ppm solution. A 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 solution and placed on a leaf of the cottom plant, all being placed 
in the hood to dry. The leaf with the treated budworm eggs is removed from 
the plant and placed in a 236.6 ml (8-oz) Dixie cup with a wet 5 cm piece 
of dental wick and covered with a lid. The 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 26.7.degree. C., 50% r.h., observations of egg hatch are made, as 
well as kill of newly hatched larvae, any inhibition of feeding, or 
interference of any sort with normal development. 
Southern Armyworm--Spodoptera 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 of 1000 ppm and 
set in the hood to dry. Following this, one leaf is placed in a 9 cm petri 
dish which contains a moist filter paper in the bottom and 10 third-instar 
armyworm larvae about 1 cm long. This dish is covered and held at 
26.7.degree. C., and 50% r.h. After 2 days, mortality counts and estimates 
of the amount of feeding are made. Compounds showing partial kill and/or 
inhibition of feeding are held for an extra day for further observations. 
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. 
Secondary Tests 
Tobacco Budworm--Heliothis virescens (Fabricius)--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 cut in 
half, and each half is placed in one of ten 29.6 ml plastic medicine cups 
containing a 1.25 cm dental wick saturated with water and one third-instar 
budworm larva is added. The cup is capped and held for 3 days at 
26.7.degree. C., 50% r.h., after which mortality counts are made. 
Compounds killing more than 75% of the larbae are further tested. 
Cabbage Looper--Trichoplusia ni (Hubner)--Third Instar 
A true leaf of a cotton plant 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 26.7.degree. C., and 50.+-.10% 
r.h. Compounds killing more than 75% of the loopers are further tested. 
Imported Fire Ant Bait Toxicant Tests (Solenopsis invicta Buren) Test 
Procedure 
Tests are conducted in 30 ml disposable plastic medicine cups (40 mm ID at 
the top, tapering to 32 mm ID at the bottom, 38 mm high). A hole (6 mm 
diam.) is drilled through the bottom of each cup and a layer of plaster of 
Paris and builders' cement (9:1 ratio) poured over the bottom. The plaster 
mixture covers the hole and acts as a wick to draw up water when the cup 
is placed on a 8 mm thick foam rubber pad saturated with water. The cups 
are placed in a tray and covered by another tray inverted to prevent rapid 
evaporation of water from the foam pad. Moisture is necessary to keep the 
humidity in the cups high and thereby prevent desiccation of the ants. The 
cement is added to make a hard mixture through which the ants cannot 
tunnel and escape. 
Twenty worker ants from field-collected colonies are placed in each test 
chamber ca. 24 hr preceding the start of the test. This pretreatment 
holding period allows time for recovery of the ants from handling and for 
orientation to the containers. 
Candidate chemicals are dissolved directly in the food material; e.g., 
soybean oil. The toxic solution is offered to the ants on cotton swabs 
saturated with the material and placed in the test chamber in small vial 
caps. Preliminary tests are conducted at concentrations of 1.0, 0.1, and 
0.01 percent. 
The ants are allowed to feed as desired on the toxic bait for 24 hr. After 
this exposure period, the toxicant is removed from the chamber and the 
ants remain without food for an additional 24 hr. At the end of this time 
new vial caps containing cottom swabs saturated with soybean oil are 
placed in the chamber and ldft for the remainder of the test period. 
Knockdown and mortality counts are made at intervals of 1, 2, 3, 6, 8, 10, 
and 14 days following initial exposure. Each test consists of 3 
replications. Room temperature is maintained at 23.9.+-.1.degree. C. 
Data obtained are reported in Table I below. 
3 TABLE I 
EVALUATION OF PENTADIENONE HYDRAZONES AS INSECTICIDES. Percent Mortality 
. Third-Instar tobacco budworm Tobacco Eggs Larvae Southern Armyworms 
Budworms Cabbage Looper 300 100 10 300 100 10 1000 100 10 7 1000 100 
1000 100 Compound ppm ppm ppm ppm ppm ppm ppm ppm ppm days ppm ppm ppm 
ppm 
##STR6## 
0 90 0 100 100 50 100 0(R) 100 90 
##STR7## 
0 100 
0 100 100 0 100 100 100 100 
##STR8## 
0 100 100 
0 100 100 0 100 30 100 100 
##STR9## 
0 90 100 90 R 90 50 
##STR10## 
0 90 80 0 100 100 0 100* 0(R) 100 100 
##STR11## 
0 90 50 0 100 100 0 R 
##STR12## 
0 0 (R) 
##STR13## 
0 0 90 
##STR14## 
0 0 0 
##STR15## 
0 0 50 
##STR16## 
0 0 100 0 R R 
R Reduced feeding; 
* = at 1000 ppm. 
Evaluation of Pentadiene Hydrazones as Insecticides. Percent Mortality at 
14 days Imported Fire Ant Compound 10,000 ppm 1000 ppm 
##STR17## 
95 87 
##STR18## 
100 97 
##STR19## 
100 36 
##STR20## 
100 25 
##STR21## 
100 95