Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
s~
This invention is directed towards novel compounds of
1,1-diphenyl-2-nitroa1kanes wherein the phenyl groups are sub-
stituted at the para position, one by alkyl and the other by
alkoxy substituents~ These new compounds are highly effective
in combatting various insect species including lepidoptera, e.g.
- southern army worm. They also possess a high degree of environ-
mental safety~being biodegradable and non-persistent in the
environment.
Since the discovery of the insecticidal properties of
DDT, scientists have endeavored to identify alternative materials
which are effective and persistent insecticides but which unlike
DDT and related chlorinated hydrocarbons biodegrade in living ,
systems to excretable metabolites.
~ Attempts at accomplishing this goal by subs~ituting
; alkyl and alkoxy substituents for chlorine in the basic diphenyl-
alkane structure of DDT and related chlorinated hydrocarbons
have been reported in the literature.
Thus the goal of identifying biodegradable insecticides
structurally similar to DDT has been achieved, but of the com- ~ -
pounds reported, none exhibit the same broad range of insecti-
cidal effectiveness as DDT. Specifically, none of the reported
biodegradable DDT - like insecticides, e.g., diphenylalkanes
containing an alkoxy or alkyl substituent, is effective at low
l ,
application rates (100 ppm or less) on the important agronomic
class of insects, lepidoptera.
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.
For example, methoxychlor which represents the DDT
basic structure with methoxy groups in the p,p' positions
instead of chlorine as reported by I.P. Kapoor, et al., J. Ag.
Food Chem., 18,1145 (1970) is biodegradable in living systems
.,
but has essentially no activity against the important lepidop
terous insect, southern army worm (see Table 1 below) even at
the high rate of 500 ppm. R. L. Metcalf et al., disclosed new
biodegradable DDT analogues possessing p-alkyl, p'-alkoxy
substituents in place of chlorine. The more effective of these
compounds as insecticides were reportedly methyl methoxychlor
and methyl ethoxychlor. Nevertheless, in our test (see Table 1
below) these compounds at the high application rate of 500 ppm,
did not control southern army worm. T. A. Jacob et al., in
J. Org. Chem. 16,1572 (1951) reported that no activity was
observed against the southern army worm when ~,p'-alkoxy
substituted diphenylnitroalknes were used as insecticides.
Additionally, U. S. Patent 2,716,627 discloses l-aryl
derivatives of 2-nitro-1-p-isopropylphenylalkanes as being
especially adapted to combat the southern army worm.-- However,
l 20 test data reported in said patent on representative compounds,
e.g., -2-nitro-1-p-isopropylphenyl-1-p-ethylphenylbutane, 2-
nitro, l,l-bis-(p-isopropylphenyl)butane and 2-nitro-l-p-isoprop7
yl-phenyl-l-tolylbutane revealed that in fact insecticidal
compositions same were totally ineffective, having zero percent
kill at application rates of 100 ppm against southern army worm
- larvae. Testing these compounds under the same test conditions
as the compounds accordiny to this
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., . . , , . . . . .~ .
7~ ~
invention revealed essentially the same results, i.e., composi-
tions containing compounds embodied in U. S. Patent 2,716,627
showed little or no effect on southern army worm laryae.
Thus the prior art indicates that DDT analogs possess-
ing alkoxy and alkyl substituents would be biodegradable but
would most likely be unable to control the lepidopterous class
of insects at economic levels of application. Therefore, quite
unexpectedly and in sharp contradistinction to these previous
compounds, the novel compounds of this invention while possess-
ing the biodegradable p-alkoxy and p-alkyl substituents are
nevertheless most effective in controlling insect species,
highly destructive of important field crops, e.g. lepidoptera.
Efective control of this class of insects, i~e., the southern
army worm has been obtained at the low economic application
rate of 100 ppm.
This invention provides a new class of compounds
;, having the following general structure:
R~
/CH-C-H
,~ R2
2 5
' .
1 ' . :
-3-
.. .. . . .. . . . . . .
: , ,, . , ,, , . :
wherein Rl is C4 alkyl branched or unbranch~a and R2 is methyl
or ethyl.
This invention also provides for the use of these
compounds in combatting insects and for insecticidally effect-
ive compositions of matter comprising at least one such
compound as insect-control agent. Unlike DDT and other related
chlorinated hydrocarbons, these compounds are biodegradable and
non-persistent in the environment. R. L. Metcalf et al.
report in the Bull. Wld. Hlth, Org., 44,363 (1971) that DDT
analogues have substituent groups (e.g. alkoxy and alkyl)
readily attacked by multifunctional oxidase enzymes present in
the environment undergo substantial biolvgical degradation
and do not appear to be readily stored or concentrated in ~ -
animal tissues or food chains. Additionally these compounds
are broadly effective in insecticidal activity against~^
- lepidoptera and coleoptera, the tlwo major classes of insects
in terms of the annual amount of damage they inflict upon
cropsO These compounds are broadl~ effective in insect
activity at low application rates, e.g~, being highly
effective against the southern army worm at application rates
of 100 ppm or 0.01~.
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39
-4-
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35~
As will be noted from the structural formula given
abo~e, the compounds according to this invention are l,l-diphen-
yl-2-nitropropanes or butanes. Non-limiting examples of
compounds of this invention include: l-(p-tert-Butylphenyl)-l-
(p-ethoxyphenyl)-2-nitrobutane; l-(p-tert-Butylphenyl)-l-
(p-ethoxyphenyl)-2-nitropropane; l-(p-Isobutylphenyl)~l-
(p-ethoxyphenyl~-2-nitropropane; l-(p-Isobutylphenyl)-l-
(p-ethoxyphenyl)-2-nitrobutane; l-(p-sec-Butylphenylj-l-
(p-ethoxyphenyl)-2-nitropropane; l-(p-sec-Butylphenyl)-l-
(p-ethoxyphenyl)-2-nitrobutane; l-(p-n-Butylphenyl l-(p-ethoxy-
phenyl)-2-nitrobutane; l-(p-n-Butylphenyl)-l-(p-ethoxyphenyl)-
2-nitropropane, 1-p-tert-amylphenyl)-1-(p-ethoxyphenyl)-2-
nitrobutane, l-(p-tert-amylphenyl)-l-(p-ethoxyphenyl)-2-
nitropropane, and others.
.
' 20
:
.,''',~ '
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In general, the compounds according to this invention
are prepared by condensing an alkoxybenzene with 2-nitro-1-
_-alkylphenyl-l-alkanol in the presence of sulfuric acid. A
solvent such as acetic acid/ carbon tetrachloride or water may
be employedD Excess alkoxybenzene may also serve as solvent.
The temperature of the reaction may vary from about -10 to
about +25.
The alkoxybenzene starting materials are commercially
available. The 2-nitro-1-p-alkylphenyl-1-alkanols may be
prepared by condensing ~-alkylbenzaldehydes with l-nitroethane,
l-nitropropane or 2-nitropropane according to standard known
procedures. The substituted benzaldehydes and the nitroalkanes
are also commercially available.
Examples 1 through 5 illustrate a convenient method
of preparing said alkanols. Examples 6 through 16 illustrate
how the nitroalkanes according to this invention are generally
prepared,
EXAMPLE 1
2-Nitro-l-(p-tert-butylphenyl)-l-butanol
~, .
A 81 g portion of ~-tert-butylbenzaldehyde was
added portionwise over 0.5 hr. to a vigorously stirred solution
of 57 g of sodium bisulfite in 500 ml of water and 200 ml
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of 95% ethanol. The resulting heterogeneous mixture was
stirred over night at ambient temperature. In a separate
flask 89 g of l-nitropropane was added slowly at 5C to a
solu~ion of 40 g of sodium hydroxide in 250 ml of 95~ ethanol
and 50 ml of water. The resulting yellow solution was stirred
at ambient temprature for 0~5 hr. before it was added drop-
wise to the above heterogeneous mixture at 5C with vigorous
stirring. The resulting slurry was then stirred over night
at ambient temperature. The reaction mixture was filtered to
remove a white solid precipita~e, and the -filtrate was diluted
with 500 ml.of water and extracted with 3 x 200 ml of ethyl
ether. The ethereal solution was washed with water and with
sa~urated aqueous bicarbonate and then stirred with saturated
sodium bisulfite until all unreacted benzldehyde was removed
` 15 as an insoluble bisulfite salt. The remaining ethereal solu-
tion was dried over magnesium sulfate and then concentrated
under vacuum to remove solvent and unreacted l-nitropropane.
The residue which crystallized on trituration with hexane was
recrystallized from hexane to afford 40 g of pro~uct: mp
86-88; ir (Kbr3 2.8 (s3, 3.4 (s), 6.5 (s3, 7.3 (s), 9.4 (m),
11.9 (s), 12.4 (m) microns; nmr (CDCl3) 7.55 to 7.20 (4H),
4.7 to 4.4 (lH, m); 4.4 to 4.2 (lH, ~), 3.0 (lH, broad),
1.95 (2H, m), 1.3 (9H, s), 0.8 (3H, m) ppm.
EX~MPLE 2
2-Nitro-l-(p-tert-but~lphenyl)-l-propanol
The procedure of Example 1 was follow~d using 81 g
of p-tert-butylbenzaldehyde, 57 g of sodium bisulfite, 75 g
.
5~
of l-nitroethane and 40 g o~ sodium hydroxide with
ethanol and water as solvents. The final product was
; recrystallized ~rom hexane to provide 33 g o~ white
crystals: mp 79-88; ir (K~r) 2.8 (s), 3.4 (s), 6~4 (s),
7.35 ~m), 9.8 (m), 11.9 (s) microns; nmr (CDC13) 7.45 to
7.15 (4Hg m), 5.0 to 4.6 (2H, m)~ 2.8 (lH, broad)~ 1.3
(6H, s), 1~4 to 1~2 (3H~ d) ppm.
EXAMPLE 3
2-Nitro-l-(p-tolyl)-l-propanol
The procedure o~ Example 1 was ~ollowed for the
reaction o~ 120 g of p-tolualdehyde and 114 g o~ sodium
bisulfite with 150 g of l-nitroethane and 80 g of sodium
hydroxide. Water was the solvent. The final product was
a yellow liquid weighing 103 g: ir (~ilm) 2.85 (m), 3.4
(m)~ 6-5 (s), 7-2 (m)~ 7.35 (m), 9.5 (m), 12.15 (m) microns;
nmr (CDC13) 7.12 (4H~ s), 5.0 to 4.5 (2H, m), 2.95 (lH, s), 2.3
(3H, s), 1.4 and 1~2 (3H~ doublet; of doublets) ppm.
.,
; EXAMPLE 4
~, 2-Nltro~ tolyl)-l-butanol
The procedure o~ Example 1 was ~ollowed ~or the
reaction o~ 120 g of ~ tolualdehyde and 114 g oS sodium
bisul~ite with 178 g of l-nitropropane and 80 g of sodlwm
hydroxide. Water and ethanol were the solvent~. The product
obtained wa~ a clear, yellow li~uid weighing 100 g: ir (~ilm)
~5 2-8 (~)~ 3~4 (m)~ 6-5 (5)~ 7,3 (m)~ 9.7 (mj, 12,2 (5) m~crons.
-8~
;
EXAMPLE 5
2-Nitro~ isopro~vlphenyl)-l-~ropanol
The procedure of Example 1 was followed for the
reaction of 74 g of _-isopropylbenzaldehyde and 57 g of
sodium bisulfite with 75 g of l-nitroethane and 40 g of
sodium hydroxide. Water and ethanol served as solvents.
The product weigh~d 41 g and was a light yellow oil which
slowly crystallized on standing: ir (film~ 2.85 (m), 3.35
(m), 6.5 (s), 7.2 (m), 7.35 (m), 905 (m), 11.95 (m) microns,
nmr (CDC13) 7.1 (4H, s), 5.0 to 4.6 (2H, m), 3.05 (lH, broad),
2.9 (lH, quintet), 1.3 (6H, d), 1.5 to 1.2 t3H, m) ppm.
EXAMPLE 6
l-(p-tert-Butylphe ~ )-2-nitrobutane
To a 90 ml portion of 98% sulfuric acid was slowly
added 33 g of phenetole at 0C. The solution was cooled to
-15 and a solution of 22.5 g of Example 1 in 66 g of phene-
tole was added dropwise over one hour at -5 to -10. The
reaction solution was stirred at -5 for 1.5 hr. and then
poured into 1 liter of ice and water. The organic products
were extracted into ethyl ether, and the ethereal solution was
washed with water, saturated bicarbonate and brine, dried
over magnesium sulfate and concentrated. Excess phenetole
was removed at the vacuum pump leaving a semi-solid residue
weighing 24 g. The residue was recrystallized twice from
hexane to yield a purified s~mple: mp 95-97; ir (KBr) 3.4
(s), 6.7 (s), 7.3 (s), 8.0 (s), 9.6 gs), 12.2 (s) microns;
nmr (CDC13)7.3 to 7.0 and 6.9 to 6.6 (8H, m), 5.3 to 5.0
(lH, m), 4.2 (lH, d), 3.8 (2H, q), 1.7 (2H, broad), 1.2
(9H, s), 0.85 (3H, t) ppm; ms (molecular ion~ 355.
, . : . , ~ :
. .
~05i~71
EXAMPLE 7
1-(p-tert-Butylphenyl)-l-(p-metho~yphenyl)-2-nitrobutane
---- _
The procedure of Example 6 was followed for the
reaction of 22.5 g of Example 1 with 90 g of anisole and
90 ml of sulfurac acid, resulting in 20 g of crude product.
A pure sample was obtained by recrystallization from heptane;
mp 114-116; ir (Ksr) 3.4 (m), 6.3 (m), 6.5 (s), 6.7 (m),
8.0 (s), 9.7 (m), 12.2 (m), 12.5 (m) microns; nmr (CDC13)
7.4 to 7.1 and 6.85 to 6.7 (8H, m), 5.35 to 5.05 (lH, m) 4.3
(lH, d), 3.6 (3H, s~, 1.95 to 1.65 (2HI m), 1.25 (9H, s),
0.9 (3H, t)ppm; ms (molecular ion) 298.
EXAMPLE 8
tert-Butvl~henvl)-1-(D-ethoxv~henyl)-2-nitropropane
The procedure of Example 6 was followed for the
reaction of 15.5 g of Example 2 with 86 g of phenetole and
85 ml of 98~ sulfuric acid, resulting in 21 g of a brown
glassy solid. All attempts at crystallization faileda ir
(film) 3.4 (m), 6.5 (s), ~.6 (m), 8.0 (s), 9.5 (m), 12.2 (m)
microns nmr (CDC13~ 7.45 to 7.05 and 6.85 to 6.65 (8H, m),
5.4 to 5.2 (lH, m), 4.3 (lH, d), 3.87 (2H, q), 1.6 to 1.2
!
(15H, m, with singlet at 1.23) ppm; ms (~olecular ion) 341.
. , ~
EXAMPLE 9
l-(p-tert-Buty1phen~l ? ~
The procedure of Example 6 was followed for the
reaction of 7.1 g of Example a with 30 g of anisole and 30 ml
of 98% sulfuric acid. The crude product (11 g) was obtained
by filtration of the reaction mixture following mi~ure with
ice and water. A purified sample was provided by recrystal-
lization from ethanol; mp 1~5-156.5C; ir (KBr) 3.35 (m),
1` - I D ~ !
,
': , ' '' ! :;,: ... .
6.5 (s), 6.6 (m), 8.05 (m), 9.7 (m), 12.2 (m) microns; nmr
(CDC13) 7.35 to 7.05 and 6.95 to 6.7 (8H, m), 5.45 to 5.15
(lH, m), 4.3 (lH, d), 3.65 (3H, s), 1.65 to 1.35 (3H, m),
1.2 (9H, s) ppm.
:` :
EXAMPLE 10
l-(p-Tolyl)-l-(p-ethoxyphenyl)-2-nitrobutane
The procedure of Example 6 was followed for the
reaction of 16.6 g of ~xample 4 with 55 g of phenetole and
50 ml of sulfuric acid. The crude product was recrystal-
lized from hexane to afford 8 g of white ~rystals: mp 92-
- 94; ir (KBr) 3.4 (m), 6.5 4s), 6.7 (m3, 8.0 (s), 9.5 (m),
12.2 (m) microns; nmr (CDC13) 7.3 to 7.1 and 6.85 to 6.7 ~
(8H, m), 5.3 to 5.0 (lH, m), 4.3 (lH, d), 3.93 (2H, q), 2.27
(3H, s), 1.95 to 1~65 (2H, m), 1.32 (3H, t), 1.02 (3H, t) ppm.
EXAMPLE 11
l-(p-Tolyl~ ani~yl)-2-nitrobutane
The procedure of Example 6 was followed for the
reaction of 16.6 g of Example 4 w~th 49 g of anisole and 50
ml of sulfuric acid. The crude product weigh~d 14.6 g and
was a viscous o11; ir (filmj 3.4 (m), 6.5 (s), 6.7 (s), 8.0
(s), 8.5 (m), 9.7 (m), 12.3 (m~ micr~ns; nmr (CDC13) 7.3 to
6.95 and 6.35 to 6.15 (8H, m)~ 5.4 to 5.0 (lH, m), 4.3 (lH,
d), 3.52 (3H, s), 2.19 (3H, s), l.9 to 1.6 (2H, m), 0.82
(3H, t) ppm.
EXAMPLE 12
l-(p-Tolyl)-l-(p-ethoxy~henyl)-2-nitr~ropane
The procedure of Example 6 was followed for the
reaction of 15.6 g of Example 3 and 55 g of phenetole in
- 11 -
, . ... . . .
50 ml of 98% sulfuric acid. The product weighed 15 g and was
a viseous liquid- ir (film) 3.4 (m), 6.5 (s), 6.65 (s), 8.05
(s), 9.55 (m), 12.3 (m) microns; nmr (CDC13) 7.3 to 6.6 (8H,
m), 5.4 to 5.15 (lH, m), 4.3 (lH, d3, 3.85 (2H, m), 2.2 (3H,
s), 1.4 (3H, t), 1.25 (3H, t) ppm.
EXAMPLE 13
l-(p-Tolyl)-l-(p-anis~1)-2-nitropropane
The procedure of Example 6 was followed for the
reaction of 15.6 g of Example 3 with 49 g of anisole and 50 ml
of 98~ sulfuric acid. Obained was 11.3 g of product as a
viscous liquid: ir (film) 3.4 ~m), 6.45 (s), 6.65 (m), 8.0
(s), 8.5 (m), 9.7 (s1, 12.3 (m3 microns; nmr (CDC13) 7.3 to
6.7 (8H, m), 5.3 (lH, doublet of quartets), 4.3 ~lH, doublet),
3.6 (3H, s), 2.2 (3H, s), 1.42 (3H, d) ppm.
EXAMP~E ~4
.. _
l-(p-Iso~ropylphen ~ -(p-anisyl)-2-nitrop-opane
.
The procedure of Example 6 was followed for the
reaction of 6.7 g of Example 5 with 30 g of anisole and 30 ml
of 98% sulfuric acid. The product was recrystallized from
hexane to afford 4.3 g o~ a white solid; mp 112-115C; ir
(KBr) 3.5 (s), 6.5 (s), 6.7 (m3, 8.0 (s), 9.5 (m), 12.3 (m)
microns; nmr (CDC13) 7.15 (s) and 6.75 (d) (8H, aromatic),
.,
4.3 (lH, quintet), 4.3 (lH, d), 3.7 (3H, s3, 2.85 (lH, -
, quintet), 1.48 (3H, d), 1.2 (6H, d) ppm.
: . .
EXAMPLE 15
l-(p-IsoE~ro~lphenyl)-l-(p-ethoxyphenyl)-2-nitropro~a-ne
The procedure of Example 6 was followed for the
reaction of 6.7 g of Example 5 with 33 g of phenetole and
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7~
30 ml of 98% sulfuric acid. The product weighed~5 g and
remained as a viscous, amber li~uid: ir (film) 3.4 (s),
6.5 (s), 8.05 (s), 9.55 (s), 12.~5 (m) microns; nmr (CDC13)
7.3 to 7.0 and 6.85 to 6.65 (8H, m), 5.3 (lH, doublet of
quartets), 4.3 (lH, doublet), 3.85 (2H, q), 2.82 (lH, quin-
tet), 1.6 to 1.0 (12H, m) ppm.
EXAMPLE 16
l-(p-Isopropylphen~ l-(p-ethoxyphenyl)-2-nitrobutane
The procedure of Example 6 was followed for the
reaction of 11.9 g of Example 5 with 24.4 g of phenetole,
~ 20 ml of 98% sulfuric acid and 20 ml of carbon tetrachloride.
- The product weighed 14 g and remained as a clear, amber,
viscous liquid: ir ~film~ 3.4 (s), 6.5 (s), 8.1 (s), 9.6
(s), 12O2 (s), 12.4 (m), microns; nmr (CDC13) 7.3 to 6.7
(8H, m), 5.2 (1~, doublet of quartei~s), 4.3 (lH, doublet),
3.9 (2H, q), 2.83 (lH, quintet), 1.78 (2H, m), 1.5 to 1.05
(9H, m), 0.9 (3H, t3 ppm.
EXAMPLE 17
In this example nitroalkanes acoording to the
invention were evaluated in standard greenhouse insecticide
tests using housefly (HF), hean aphid (BA), Mexican bean
beetle (MB) and southern army worm (SA). The rates of appli-
cation were 500, 200 and 100 ppm of active ingredient.
The results are as set forth in Table 1 below. DDT type
compounds: methoxychlor, meth~l methoxychlor and methyl
ethoxychlor were also evaluated, and under identical test
conditions.
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TABLE 1
COMPOUND ~ HF BA MB SA
Example 6 500 100 70 100 100
. 200 ~ 100 100
100 100 40 100 100
Example 7 500 10 80 100 50
200 ~ 100 --
100 -- 60 100 10
Example 8 500 100 100 100 100
200 -- 100 100 40
100 -- 100 100 20
Example 9 500 80 10 40 10
200 - - ~
~' 100 __ __ __ __
15 Example 10 500 100 70 100 10
200 __ __ _ __
100 -- 10 40 --
`, Example 11 500 70 70 10 10
200 __ __ __ __
100 --- -- _ __
', Example 12 500 100 10 100 10
200 ~
100 --- -- 100 ---
Example 13 500 100 10 100 10
200 __ __ __ __
: 25 100 __ __ 50 __
Example 14 500 100 10 100 10
2 0 0 ~
100 -- -- 60 --
Example 15 500 100 go 100 80
~00 -- 10 -- 10
. 100 -- 10 100 ~0
Example 16 500 100 100 100 100
200 -- -- 100 100
100 100 -- 100 ~0
Methoxychlor 500 30 100 100 10
200 ~_ __ __ __
100 -- 10 100 10
-15-
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COMPOUND RATE (~m~ HF BA MB SA
Methyl methoxychlor 500 100 100 100 10
; 200 __ __ __ __
100 10 10 100 10
Methyl ethoxychlor 500 90 100 100 10
200 ~_ __ __ __
100 10 10 100 10
Test Methods:
. _ . . _ _ _
; House Fly; 1 millimeter of an aqueous solution or
suspension of the test compo~nd was pipeted into a 9 cm. petri
dish containing filter paper and 0~1 gram Or granular sugar.
Ten adult house flies were admikted and the dish closed.
Observations were made periodically for knockdown and at 24
houræ ~or mortality. Mortality was primarily caused by
~, 15 stomach poisoning.
:,~
Bean Aphid; adult bean aphids on nasturtium cuttings
to encourage confinement, were contained in speciall~
designed 100 millimeter screenecl cages and exposed to sprays
at 15 psi of 10.0 milliliters of` an acetone solution of the
,~ 20 kest compound. The test cages were mounted on a turntable
rotating at 30 rpm in a wind tunnel. When dry, the petioles
o~ the treated leaves were placed in a water-filled pla~tic
conkainer on a speclally constructed holding sta,nd. This
was necessary in order to keep the treated leaves turgid
~or the duration o~ the test. All the tests were r~n in
duplicate with ken or more aphids in each cage, An initial
concentration of 500 ppm was used and then the candidate
compound was retesked at 200 and 100 ppm. Mortality was
recorded after 24 houræ, with all tests run In dupllcate.
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Southern army worm and Mexican Bean Beetle; lima
bean leaves of uniform size were momentarily dipped in a water-
acetone solution of the test compound and the treated leaves
; were then placed on moistened ~ilter paper in 9 cm. petri
dishes and allowed to air dry. When dry, five, third,
or fourth instar larvae were introduced and encouraged to
feed on the treated follage by means o~ confinement.
The dishes were closéd and held for observation o~ mortality
and ~eed during a ~8 to 72 hour period.
From the data and the table, it will be noted (1)
that compounds embodied by the present invention have a
broad range o~ insect-control activity, and also exhibit
considrable insect-control activity at low rates o~ application,
~- (2) the DDT type compounds tested ~or all practical purposes
did not exhibit a broad range o~` insect-control activity and
were essentially ineffective against southern army worm at
~- the low application rate (100 ppm). In particular, markedly
effective against southern army worm is the compound of
Example 6 (~amely, l-(p-tert-~ut~lphenyl)-l-(p-ethoxyphenyl)-
2-nltrobutane) that was 100~ e~fective at 100 ppm.
~ ',
The compou~ds embodied herein may be used in ~tarious
ways to achieve ef~ective insect control. They can be applied
per se, as solids or in vaporized ~orm, but are pre~erably
applied as the toxic components in insect control com-
posltions of a compound and an inert solid or liquid
carrier. Th~ compositlons c~n al~o be applied as dust,
as liquid sprays, or as gas-propelled sprays and can
contain, in additio~ to a carrier, additives such as emulsifying
agents, wettin~ agents, binding agents, gàses compressed thro~h
the liquid sta~e, odor~nts, stabiliæers and the like. A wide
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variety o~ liquid and solld carriers C~l be u~ed in the
insect control compositions. Non-limiting examples of
liquid carriers, include wa~er; organic solvents such as
alcohols, ketones, amides and esters; mineral oils such
as kerosene, light oils, medium oils; and vegetable oils
such as cottonseed oil, Non-limlting examples of solid
carriers include talc, bentonlte, diatomaceous earth,
pyrophyllite, fuller~ earth, gypsum, flours derived from
cottonseeds and nutshells, and various natural and synthetic
clays having a pH not exceedlng about 9.5
The amount of compounds of this invention utilized
in insect control compositions will vary rather widely. It
depends to some extent upon the type of composition in which
the material is being used, the natura o~ the condition to
be controlledg and the method of application (i.e., ~praying,
du~ting~ etc,). In the ultimate in~ect control composition
a~ applied ln the field, insect control agent concentratlons
a~ low a~ 0.0001 weight percent of the total composition can
be used. In general~ compositions containing ~rom about
0.01 - 0.05 weight percent in~ect control agent in either
liquid or ~olid carrier give excellent results. In ~ome case~g
however3 stronger dosages of up to about 10 weight percent
may be required,
In practice composition~ ~or controlling insects
utillælng the~e compounds are u~ually prepared in the form of
concentrate~ which are diluted in the field to the concen-
tration de~ired ~or application. For example, the concentrate
can be a wettable powder containing large amount~
of a compound according to thi~ invention, a carrier
e. g " attapul~ite or other clay), and wetting
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7~
and dispersing agents. Such a powder can be diluted prier
to application by dispersing it in water to obtain a spray-
able suspensi~n c~ntaining the concentration ~f insect con-
trol agent desired for application. Other concentrates can
be selutions that can be later diluted~ e.g., with kerosene.
Thus, it is within the contemplation Df this invention to
provide compositions combining superior insect activit~ with
enviornmental safety~ such c~mpositions may contain up to
about 80~, by weight, of the composition of an insecticidal-
ly-active cempound according to this invention. Accordingly,
depending upon whekher it is ready for application or it is
in concentrated form the contemplated insect control compo-
sitions may contain between about 0.0001~ and about 80~, by
weight of the compositi~n, ofan insecticidally-effective com-
pound of this invention and a liquid or solid carrier as de-
fined hereinaboveO
Thus, this invention in addition to the new class
of novel compounds described hereinabove and preferred embodi-
ments thereo~ such as, l-(p-tert--Butylphenyl)-l-(p-ethoxyphenyl)-2-
nitr~butane, 1-(p-tert-But~lphen~l)-1-(p-ethoxyphenyl)-2-nitro-
prop~ne, and l~(p-Isopropylphenyl)-l-(p-ethoxyphenyl)-2-nitr~butane
also provides for a method of insect control comprising ap~
plying to the insect or its enuironment at least one compound
or composition thereo~ according to this invention in effective
~5 amounts to obtain said control.
Although the present invention has been described
with preferred embodiments, lt is to be understood that
modifications and variations may be resorted to while not
departing from the spirit and scope of the invention.
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