Preliminary tests with certain N-substituted piperonylamides for synergistic action in allethrin fly sprays

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Material Information

Title:
Preliminary tests with certain N-substituted piperonylamides for synergistic action in allethrin fly sprays
Physical Description:
6 p. : ; 27 cm.
Language:
English
Creator:
Gersdorff, W. A ( Wilbur August ), b. 1894
Mitlin, Norman
Gertler, S. I
United States -- Bureau of Entomology and Plant Quarantine
Publisher:
U.S. Dept. of Agriculture, Agricultural Research Administration, Bureau of Entomology and Plant Quarantine
Place of Publication:
Washington, D.C
Publication Date:

Subjects

Subjects / Keywords:
Flies -- Control   ( lcsh )
Allethrin   ( lcsh )
Amides   ( lcsh )
Genre:
bibliography   ( marcgt )
federal government publication   ( marcgt )
non-fiction   ( marcgt )

Notes

Bibliography:
Includes bibliographical references (p. 4).
General Note:
Caption title.
General Note:
"E-848."
General Note:
"October 1952."
Statement of Responsibility:
by W.A. Gersdorff, Norman Mitlin, and S.I. Gertler.

Record Information

Source Institution:
University of Florida
Rights Management:
All applicable rights reserved by the source institution and holding location.
Resource Identifier:
aleph - 030339345
oclc - 780665177
System ID:
AA00025251:00001

Full Text



LIBRARY
STATE PLANT DOARD
United States Department of Agriculture
Agricultural Research Administration
Bureau of Entomology and Plant Quarantine



PRELIMINARY TESTS WITH CERTAIN N-SUBSrIITUTED
PIPERONYLAMIDES FOR SYNERGISTIC ACTION IN
ALLETHRIN FLY SPRAYS

By W. A. Gersdorff, Norman Mitlin, and S. I. Gertler
Division of Insecticide Investigations


In previous work seeking synergists for pyrethrum in fly sprays it
was found that certain N-substituted piperonylamides exhibited synergistic
action when used in combination with pyrethrum solutions (Gertler et al. 3).
The relative effectiveness of some of the best of these compounds was later
determined (Gersdorff and Gertler 2). In the research described herein
the joint action of compounds in this group and allethrin was studied.
These amides contain the methylenedioxyphenyl group appearing in
most of the effective pyrethrum synergists. They have the general
formula
0
,, /R
H2C C N\R'
\0


R and R' may be hydrogen or an alkyl or cyclic group. When both are
hydrogen, the compound is piperonylamide. The cyclic group may be
substituted or unsubstituted. The compounds were prepared by reacting
piperonyl chloride with the selected amines according to recognized
procedures. They were all purified.
The compounds were incorporated in oil sprays, alone and in mixtures
with 0.5 mg. of allethrin per milliliter. Even though acetone was used as
an auxiliary solvent, the solubility of some of the compounds was so low
that the desired concentration of the adjunct of 5 mg. per milliliter could
not be attained. For these materials the concentration was 2.5 mg. per
milliliter. The proportion of acetone to refined kerosene was 1 to 3 for
all sprays.
Allethrin standards were prepared at concentrations of 0.25, 0.5, and
1 mg. per milliliter. The allethrin used was from a distilled sample of
high purity (94 percent by the hydrogenolysis method).


1_/ Previous publications in this series are E-805, E-828, and E-837.


October 1952


E-848





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The tests were made by the Campbell turntable method on adult house
flies (Musca domestic L.) reared by standard laboratory procedure.
Since knock-down of flies is increased by the addition of acetone, it was
not estimated. Mortality only was determined for each spray. Approx-
imately 100 flies averaging 3 1/2 days in age were used in each test. The
mixed sprays were replicated four times, the sprays containing the
adjuncts alone but twice. Since it was necessary to make the tests in
several series, each with a different population of flies,, mortalities in
the different series would not be directly comparable. Therefore,the
allethrin standard sprays were included in each series.
The adjuncts alone were nontoxic at the concer.trations used. The
mean mortalities obtained with the other sprays are given in table 1.
A regression equation for the allethrin standards was obtained from the
data in each series by the method of probit analysis as described by
Finney (1). From this equation the logarithm of the allethrin equivalent
was calculated for each of the four mortalities for all materials. From
an analysis of variance of these log concentrations the allethrin equivalent
required to show a significant increase in toxicity was calculated. The
mean allethrin equivalents and those required to demonstrate synergism
are also given. By comparison of the allethrin equivalent with the actual
amount of allethrin in the mixture, 0.5 mg. per milliliter, ratios of
toxicity may be obtained. Therefore, multiplying the allethrin equivalent
by 2 gives the toxicity of the mixture relative to allethrin.
Since the adjuncts alone were nontoxic at the concentrations used,
any significant increase in toxicity over that of the allethrin in each
mixture may be ascribed to s Kergistic action. All the mixtures except
one showed such an increase. Those for which the relative toxicity based
on the allethrin equivalent was three or more times the expected contained
the following amides:

N-benzylpiperonylamide
N -(o -bromophenyl) piperonylam ide
N -butylpiperonylamide
N- cyclohexylpiperonylam ide
N,N dibenzylpiperonylamide
N,N-diethylpiperonylamide
N ethylpiperonylam ide
N -(o nitrophenyl)piperonylamide
N -phenylpiperonylamide
N -propylpiperonylamide
N-nm-tolylpiperonylamide
N o tolypiperonylam ide





-3-


The mixtures for which the relative toxicity was about twice the
expected contained the following amides:

N-amylpiperonylamide
N-(m -bromophenyl)piperonylamide
N-(m-chlorophenyl)piperonylamide
N-(o- chlorophenyl) piperonylamide
N-methylpiperonylamide
N-p-tolylpiperonylamide

For four mixtures the increase in toxicity was less than twice the
expected but still significant. The adjuncts in these mixtures were as
follows:

N-(p-bromophenyl)piperonylamide
N-(p-chlorophenyl)piperonylamide
N-1 -naphthylpiperonylamide
N-2-naphthylpiperonylamide

With the second and third compounds the increase in toxicity of the mix-
ture was on the borderline of significance.
Unsubstituted piperonylamide was the only compound not affecting the
toxicity when applied jointly with allethrin under these conditions.
It is not safe to attempt to estimate relative toxicity of compounds in
the first groups precisely, because of too great extension of the standard
curves beyond the highest concentration tested. Extrapolated points are
too greatly affected by the slope of the determined curve. However, one
of the compounds in this group, NN-diethylpiperonylamide, was also one
of the most effective in pyrethrum mixtures (Gersdorff and Gertler 2).
The least effective of the N-monoalkyl-substituted compounds was
the methyl derivative.
The ortho-substituted compound was the most effective of the tolyl
derivatives, and the para isomer the least. The same was true for the
bromophenyl derivatives, but with the chlorophenyl derivatives the meta
isomer was as effective as the ortho isomer. Gertler et al. (3) reported
that in mixtures with pyrethrins tested by the same method the ortho-
substituted aromatic piperonylamides appeared to be more effective than
the corresponding meta or para derivatives.
Substitution of bromine in the ortho position on the phenyl derivative
did not give a compound significantly different in effectiveness from the
phenyl derivative itself. Substitution of chlorine, on the other hand, re-
sulted in considerable decrease in effectiveness. The nitro group in this
position on the phenyl derivative gave a synergist not so effective as the
phenyl derivative but more effective than the corresponding chlorophenyl
compound.




-_4-


Methyl-substituted N-phenyl piperonylamides were more effective
synergists than the other corresponding substituted phenyl derivatives.


Literature Cited

(1) Finney, D. J.
1952. Probit analysis. 318 pp. Cambridge.

(2) Gersdorff, W. A., and Gertler, S. I.
1944. Toxicity to house flies of certain N-substituted piperonyl-
amides and benzamides combined with pyrethrins in oil
base insect sprays. Soap and Sanit. Chem. 20(2): 123,
125.

(3) Gertler, S. I., Fales, J. H., and H.IIer, H. L.
1943. A study of the synergistic action of N-sub-ti' 'ed
piperonylamides when incor' ., ,rated in .:y spra -.
Soap and Sanit. Chemrn. 19(4): 105, 107.





-5-


Table 1. --Toxicity to house flies of space sprays containing certain
N-substituted piperonylamides mixed with allethrin. Concentration
of allethrin 0.5 mrg., and of amides 5 mg. per milliliter unless other-
wise indicated


Mean Mean
Adjunct mortality allethrin
in 1 day equivalent


Percent


Mg. per ml.


Series 1

Piperonylamide-
Piperonylamide, N-butyl-
N-phenyl-
N-m-tolyl
N-o-tolyl-
Allethrin standard, 1.0 mg. per ml.
0.5
.25


Required to demonstrate synergism


Series 2


Piperonylamide,


N-o-chlorophenyl-
N-cyclohexyl-
N- I -naphthyl--1
N- 2 naphthyl-


N-p-tolyl-
Allethrin standard, 1.0 mg. per ml.
0.5
.25


Required to demonstrate synergism ----


Series 3


Piperonylamide, N-benzyl-
N-p- chlorophenyl-1/
N- ethyl-
N-methyl-
N-propyl-
Allethrin standard, 1.0 mg. per ml.
0.5
.25


76.8
50.3
87.2
71.8
93.9
67.6
37.9
12.6


Required to demonstrate synergism --


1.298
0.672
1.854
1.106
72
1.007
0.507
.241
-- .690


42.6
82.4
86.2
76.0
98.9
65.6
41.4
15.8


0.540
1.880
2.164
1.339
>2
0.972
.522
.214
.769


50.6
67.2
32.7
44.7
50.1
53.1
27.7
5.3


0.927
1.341
0.628
.833
.916
.976
.521
.230
.639





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UNIVERSITY OF FLOOR DA
11 11 I 1I 1 1 11 1
3 1262 09239 6604


Table 1. --Continued.


Mean Mean
Adjunct mortality allethrin
in 1 day equivalent

Percent Mg. per ml.

Series 4

Piper', iivlamide, N-amyl- 70.1 1.181
N-(m-bromophenyl)- 66.8 1.107
N-(o-bromophenyl)- 91.1 >2
N-(m-chlorophenyl)- 59.3 0.944
N, N-diethyl- 97.1 >2
Allethrin standard, 1.0 mg. per ml. 62.7 1.016
0.5 26.6 0.495
.25 6.1 .237
Required to demonstrate s, -ergis, .649

Series 5

Piperonylamide, N-(p-bromophenyl) -_-- 42.9 0.695
N,N-dibenzyl- 82.5 1.647
N-(o-nitrophenyl)- 83.1 1.638
Allethrin standard, 1.0 mg. per ml. 58.1 0.928
0.5 35.2 .596
.25 4.0 .182
Required to demonstrate synergism .668


I/ 2.5 mg. per ml.