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Патент USA US2123928

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Patented July 19,1938
'
meters
UNITED STATES PATENT
2,123,928
STABILIZED PARASITICIDAL COMO
SITION
_
Euclid W. Bousquet, Wilmington, Del., assignor, ‘ I
by mesne assignments, to E. I. du Pont de
Nemours & Company, Wilmington, DeL, a cor
poration of Delaware
‘
No Drawing. Application ‘January 6, 1936,
Serial No. 57,780
11 Claims. (01. 167-30)
The present invention relates to thio-diarylamine parasiticidal compositions stabilized by the
addition thereto of certain sulfur compounds derived from sulfur acids of an oxidation stage
5 lower than sulfuric acid.
form showing the —S—H group, are particu
larly eflicient in my invention.
_ Among the organic sulfur compounds I obtain
very useful stabilization with, for instance, mer
captans, such as mercaptobenzothiazole, octyl '5
Thio-diarylamine parasiticides readilydeterio~
mercaptan, lauryl mercaptan, thio—beta—naph—
rate when exposed to atmospheric conditions and}
thol, thiourea, thioamides, diphenyl-thiourea, etc.
gradually lose their toxicity and efficiency. It
Among the stable, reducing derivatives of the
was, for instance, found that a thio-diphenyl- lower sulfur-oxygen acids, I found that their
10 amine insecticide lost 60% of its activity in killing vammonia, alkali-metal, amine, or other metal 10
insects when exposed in the open airfive days.
salts are readily available and useful in my in~
_
I have found that parasiticidal compositions,
based on thio-diarylamines which contain minor
amounts, for instance, from 1 to 10% ?gured on
15 the thio-diarylamine present, of a stable, reducing derivative of a lower sulfur acid, do not lose
their parasiticidal e?iciency in the same degree
when exposed to atmospheric conditions.
In generalIprefer to use neutral or only slight-
3“ ly basic, 1. e., non-acidic compounds or deriva-
vention.
They are stable under the conditions of ex
posure to the atmosphere at which they are used
according to my invention. Besides these salts, l5
their aldehyde and ketone derivatives are like
wise very efficient for stabilizing thio-diarylaminc
parasiticides. Among the numerous compounds
of this type which I contemplate admixing with
‘
thio-diarylamine compositions I wish to list the 2"
tives of lower sulfur acid compounds which I ad-
following: sodium or potassium sul?tes; ammoni
mix with the thio-diarylamine to stabilize the
um, sodium, potassium thiosulfates; ammonium,
latter’s toxicity.
.
sodium, potassium, zinc hydrosul?tes (in this
The lower sulfur acids, the derivatives of which ‘ connection I use the expression hydro sul?tes in
‘35 are useful in my invention, are mainly sulfurous preference to “hypo” sul?tes, in view of the fact 2'
acid, E803, thio-sulfurous acid H2S2O7, hydrosulfurous acid H2S2O4, the polythionic acids, hydrogen sul?d, etc. '- The free acids themselves are
mostly unstable or volatile and it is only their30 stable derivatives which display a distinct reducing action in aqueous media which are contemplated for use as stabilizing agents for thio-diarylamine parasiticides.
Another common characteristic of these sulfur
35 compounds is their reducing action in aqueous
media. This reducing action is, for example,
shown by their action on quinonic dyestuffs which
are transformed into leuco-compounds by the
_action of such sulfur compounds, methylene blue
40 bejngadyestu? which is easily reducedtoa'leucm
compound by thesulfm- compounds of my invem
tion_ Broadly Speaking, these Sulfur compounds
are also capable of acting upon discolored thim
45 diphenylamine which’ for instance, has been
that this latter expression is still used, particu
larly in commercial practice,‘ to designate thic
sulfates M2S2O7, and this double use might lead
to confusion); the aldehyde derivatives of the
hydrosul?tes, for instance, sodium or zinc for» 3G
maldehyde-sulfoxylates; and the alkali metal
polythionates.
The above includes substances of this type
which are commonly available commercially, but
it will be understood that my invention is not 3.3
limited to the use of the commercially available
substances.
,
it was found that thio-diarylamine parasiti
cides become greenish 01‘ bluish 011 8111308111? ‘~50
the atmosphere, and that with this change of to
color towards the short wave length end of the
spectrum, the toxicity correspondingly dimin~
lshes. When this discoloration is prevented or
wheirthe thio-diphenylamine is treated with a
transformed by oxidation into a green compound
feducmg. .sulfur compmtnd .88 desqnbeq he.rem’ 45
to restore its original color.
252M232?o?frgggrggm'dmrylamme 3'5 ember
The derivatives of hydrogen sul?d which are
sufliciently stable, have reducing properties and
.
. .
.
_
_ ’
50 are available for the stabilization of thio-diphen-
ylamine parasiticides, include water soluble sul_
?des, Such as the alkall metal, barium, 6110- $111-‘?des, but I found that organic compounds con
taining the sulfhydryl, —S—H group, or organic
55 sulfur compounds which can exist in a tautomeric
-
'
-
.
.
.
adIn- the “Peruse of my mv-emlon I {minutely
mix a minor amount, for instance, mom 1
107 of a reducin sulfur
a
g
d
'
t
-
to
-
compoun wlth he thlo" v0
diarylamine and when sprayed on vegetation it
will be found that the composition remains e?i~
cient without discoloration for a much longer
period than a parasiticide containing no such in
activation inhibitor. For most purposes, ‘i1 pre- 55
a;
2,123,92E
fer to use 8.
though
amines are all
characterized by containing the
heterocyclic nucleus
soluble compounds which, on evaporation of the
water of the spray, will deposit upon the particles
of the insoluble thio-diarylamine.
A very simple and e?icient manner of testing a
given sulfur compound for its availability as an
atmospheric inactivation inhibitor for thio-di
in which R and R1
which two adjac are aromatic nuclei in each of
forming the bet ent carbon atoms take part in
arylamine parasiticides is as follows:
A few drops of an aqueous ferric chloride solu
tion is added to a solution of thio-diphenylamine
in acetone: the solution turns immediately green.
15 When the acetone solution contains a small
Some of the hydrogen atoms
to R and R1
amount of a reducing sulfur compound as de
scribed herein, no such green coloration develops.
20
parasiticides.
,
In this test I found, for instance, that the dis
coloration by ferric chloride of a
erocyclic carbon-nitroaen-sulfur
ring.
ogen, nitro, amine, alkoxy
which do not impart water s or aryloxy groups,
olubility to the com
pounds.
These parasiticidal compositions are
used in
aqueous suspensi on as sprayswhich
include com
monly spreading, emulsifying,
or wetting out
agents, or as dry
in admixture with inert
substances, such asdusts
talc, foraminiferous powders
and others.
25
mercaptan,
lauryl mercaptan, thio-urea, thio~beta-naphthol,
30
diphenyl--thiourea, other substituted thioureas, a
thioamide, a formaldehyde sulfoxylate, sodium
sui?te, sodium thiosulfate, sodium hydrosul?te,
etc.
These compounds have also been found to in
hibit the atmospheric inactivation of thio-diphen
ylamine and other thi-diarylamine parasiti
cides.
35
40
in ‘which R. and R1 are aromatic nuclei.
The proto type of these compounds is thio-di
phenylamine, which is produced, for instance, by
heating diphenylamine with sulfur
of a catalyst, such as aluminum chloride, ferric
chloride, iodine, etc.
-
Other members of the novel group of insecti
cides according to my invention are the thio com
pounds obtained by the action of sulfur upon
55
diarylamines such as, for instance, those obtained
from phenyi-alpha-naphthyl amine which pre
my novel inactivation inhi
lowing:
Apples were sprayed with a parasiticidal com- .
position of three pounds thio-diphenylaminé in
water ‘which contained
wetting agent, a
11 another set 1
was added to ‘the spray. In
e apples were infected with cod
sumably has the formula
below:
H
N
60
UIH4<B 9010111
or from phenyl-beta-naphthylamine,
65
di-alpha-naphthylamine,
di-beta-naphthylamine,
di-biphenylamine,
N, N-di-alpha-naphthyl-para phenylene-dia
mine,
N, N-di—biphenyl-metaphenylene-diamine,
N,
N-di—pheny-metaphenylene-diamine,
N, N-di-phenyl-benzidine,
p, p'-di-(pheny1-amino) di-phenylamine.
75
'
_
Per cent control
g
_
Composition
Apples
Apples
ate" in_
63%;”
iectod
r
spray
immedp infected
,
Percent
Percent
improvo~
iosso!‘
initial
e?lcxoncy
went over
o0
unstabil
iud
ma
W
.
N, N-diphenyl-p-phenylenediamine,
70
-
\
Thio-diphcnylamine.
Thio-diphenyiamino
53
40 __________ _
72
‘M
66
5% men-capto
benzothiazoie ____ ._
I claim:
91
86
70
' 1. A parasiticid
thio-diarylamine
The thio derivatives obtained from these diaryl
_\\
,
3
2,128,928
2. A parasiticidal composition comprising a
thio-diarylamine as the active parasiticidal in
gredient stabilized by a stable derivative of a
sulfur acid of an oxidation stage lower than that
of sulfuric acid, said derivative having the prop
erty of inhibiting the discoloration toward green
when present in an acetone solution of thio-di
phenylamlne on addition thereto of ferric chlo
ride.
3. A parasiticidal composition comprising a
thio-diarylamine as the active parasiticidal in
gredient stabilized by a non-acidic, stable, reduc
ing derivative of a lower sulfur-oxygen acid.
4. A parasiticidal composition comprising a
- thio-diphenylamine as the active parasiticidal in
gredient stabilized. by a sulfhydryi compound
which has reducing properties and is able to react
with thio-diphenylamine which has become of a
green color by the action of atmospheric ex
posure to restore its color.
5. A parasiticidal composition comprising a
thio-diphenylamine as the active parasiticidal in—
gredient stabilized by a stable organic compound
having reducing properties and containing a sul
fur-containing group in which an -S—H group‘
is at least reactively available.
6. A parasiticidal composition comprising a
thio-diarylamine as the active parasiticidal in
gredient stabilized by a stable reducing deriva
tive of a sulfur acid of an oxidation stage lower
than that of sulfuric acid containing a sulfhydryl
group.
- '7. A parasiticidal composition comprising a
thio-diarylamine as the active parasiticidal in
gredient stabilized by a stable reducing deriva
tive of a sulfur acid of an oxidation stage lower 10
than that of sulfuric acid containing a sulfur
containing group in which an --S-—H group is at
least reactively available.
8. A parasiticidal composition comprising thio
diphenylamine stabilized. by a hydrosul?te.
9. A parasiticidal composition comprising thio
diphenylamine stabilized by a mercaptobenzothi
azole.
10. A parasiticidal composition comprising
thio-diphenylamine stabilized by a thiourea.
11. A parasiticidal composition comprising
thio-diphenylamine stabilized by sodium hydro
sul?te.
‘
EUCLID W. BOUSQUET.
20
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