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Патент USA US3070503

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3,070,493
"ice
United States
Patented Dec. 25. 1962
2.
1
lyzed as 10.0% P‘ and 21.6% S compared to 10.7% P
3,070,493
and 22.1% S theoretical for
'
‘
PHOSPHORO CARBIMIDATES
NCaHs
Glenn R. Price, South Chicago Heights, and Edward N.
Walsh, Chicago Heights, 111., and James T. Hallett,
(02H5o.)a1>.(0)—s-s~0
Saratoga, Cali?, assignors to Stau?er Chemical Com
002E‘
pauy, New York, N.Y., a corporation of Delaware
EXAMPLE 2
No Drawing. Filed Apr. 10, 1961, Ser. No. 101,673
23 Claims. (Cl. 167-30)
Following the procedure of Example 1, but using N-p
This invention relates to .a new class of phosphor-us 10 chlorophenyl-O-ethyl thiocarbam-ate, 36 grams (96%) of
containing pesticides ‘and a process for utilizing the same.
(oiHtmrr(0)-1s_s_o=NotHio1
In particular this invention relates to new compounds
(I) CzHs
having a novel disul?de con?guration which provides new
was prepared which analyzed 7.4% P and 16.0% S com
and valuable characteristics. These new compounds have
pared to 8.1% P and 16.7% S theoretical.
I
been found to be useful in the elimination and control of
EXAMPLE
3
numerous insect pests as will be shown hereafter.
These new compounds are phosphoro carbimidates
Following the procedure of Example 1 but using ‘N
which may be represented by the formula:
R10 0
phenyl-O-methyl thiocarbamate, 60.0 grams (92%) of
NR3
(G2H5O)2—'P(O)~S~—S—C=NC0H5
20
CH3
was prepared which had an index of refraction
ND25=\1.5540
wherein R1 and R2 are the same or ‘di?erent alkyl redicals,
R3 may be alkyl or iaryl, R4 may be alkyl or aryl and X is
oxygen or sulfur. They may be prepared according to the
and analyzed 8.6% P and 18.7% S compared to 9.25%
P and 19.1% S theoretical.
following general reaction:
v
(R10)
EXiAM-PLE'4
In [a similar manner but using N-phenyle‘O-isopropyl
thiocarbamate, a 90% yield of‘ product was obtained.
P(O)SY + RgNHC (S)XR4 + REN __’
This material analyzed as 8.55% P and 17.4% S com
(R20)
(R10)
P (O)—S——S—C
%
(R20)
pared with 8.5% P and 17.6% S theoretical for
NR3
C2H50)2P_(O)—S—S—C=NCBH5
OC3H1
EXAMPLE 5
-|- RsN-HY
X34
wherein R1, R2, R3, R4 and X are as de?ned above, Y is a
halogen, and R5N is a tertiary amine hydrogen halide ac
_Following the procedure of Example 1 but using ‘0,0
ceptor.
dimethylphosphorosulfenyl chloride, 57 grams (93%
Among the alkyl radicals which we have found suitable
for the phosphorus ester portion of the molecule are the 40
yield) of
methyl, ethyl, propyl, butyl, ‘octyl, and decyl radicals as
well as combinations resulting in mixed esters such as
methyl ethyl, ethyl octyl, methyl, butyl, ethyl propyl and
the like. Suitable alkyl or aryl radicals for R3 and R4
include methyl, ethyl, propyl, butyl, octyl, phenyl, chloro
45
-
<OH.o)iP(0)-s‘-s—o=NCiH.
OCzHa
was prepared which analyzed as 8.9% P 18.8% S
compared with 9.65% P and 19.9% S theoretical.
EXAMPLE 6
phenyl, nitrophenyl and the like.
The hydrogen halide acceptor may be any of the well
known alkaline compounds suitable for this use. In par
ticular we prefer to use tertiary amines such as pyridine,
triethyl‘amine, trimethylamine and the like.
In a similar manner
(CBHUOMP (O)—s—-S—C:NC6H5
60
The process is preferably carried out in ‘an inert solvent
in the presence of the hydrogen halide acceptor by adding
approximately stoichiometric amounts of 0,0-dialkyl
O CH:
was made in 84.5% yield, ND35=1.5-1:24, ‘analysis 6.05%
P and 12.5% S (theoretical 6.16% P, 12.7%. S).
phosphorosulfenyl halide to the appropriate thiocarba 55
mate. The reaction is nearly instantaneous at tempera
EXAMPLE 7
The following examples illustrate the compounds of
EXAMPLE 8
In a similar manner
tures from about 0° C. to ordinary room temperature, al
(CsHnO) (021350) P (O).-——S -—S —C=NCOH5
though it is best to stir the ?nal thickened reaction mixture
for a short while to ensure complete reaction. The prod~
0 011(0113):
not is then recovered by ?ltering ‘off the halide salt or by
60 was made in 99% yield, ND25=1.5176.
other well-known means such as washing out the salt.
our invention:
To a solution of 29.7 grams of N-phenyl-S-ethyl‘ dithio
EXAMPLE 1
c-arbamate in 150 ml. of ether was added 15.2 grams of
To a solution of 7.9 grams voi:'-pyridine and 18.1 grams 65 .triethylarnine. The solution was cooled to 10° C. and
30.6 grams of 0,0-diethylphosphorosulfenyl chloride was
of N-phenyl-O-ethyl-thiocarbamate in 200 cc. 'of ether
added over a 30 minute period. The reaction mixture was
was added 20.4 grams of 0,0-diethylphosphorosulfenyl
chloride over a 30 minute period at 10° C. The crude
product was stirred for two hours at room temperature
and then ?ltered to, remove the pyridine hydrochloride.
The crude product was stabilized to 50° C. at 1.0 mm. of
Hg to yield 30.5 grams (87% yield). The product ana
stirred for an additional hour at room temperature and
then at re?ux for 30 minutes. After ?ltering and remov
ing the solvent, the product was stabilized to 50° C. at 1.0
mm. Hg pressure. A yield of 51.5 grams (95.5%) was
obtained with an index of refraction ND25‘==1.5802 and
3,070,493
11
water.” The latter contains 2.5 grams of Vatsol and 1.0
gram of Methocel per 20 liters of water. Each solution
is then sprayed onto the insects using a DeVilbiss hand
sprayer in a fume hood. Mortality is reported after 72
hours as percent kill/percent concentration.
Q
which analyzed 7.32% P and 26.4% S compared to
8.5% P and 26.3% S for
(CzH5O)zP(O)-—S-—S—C=NC5H5
SCzHt
EXAMPLE v9
In addition to the above insects, tests were also run
on the two-spotted mite, Tetranychus telarius (designated
Following the procedure of Example 8, but using N
phenyl-S-butyl dithiocarbamate, 51.0 grams of
(C2HsO)IP(O)-—S—-S~—C=NCeHa
28M) and the effects were additionally noted on the eggs
(designated 2SME). The tests were conducted by in
10
festing young Pinto bean plants in the primary leaf stage
with several hundred mites. The infested plants were
then sprayed to run-off using the sprayer and solutions
previously described. The results are again reported as
ND25= l .5704
percent kill/percent concentration. The miticidal activ
and analyzed as 7.5% P and 25.2% S compared to 8.5% 15 ity is determined after seven days but the ovicidal results
require fourteen days.
P and 26.3% S theoretical.
The following results were obtained using the com
Using the process as outlined above the following addi
pounds of this invention.
tional compounds were made.
s 048:9
was prepared which had an index of refraction
“A
Theoretical
Example
R;
R:
R:
.9 E
X
B4
N 1:25
Per
cent S
Per
om
The class of compounds characterized by the foregoing
examples has been found to have valuable pesticidal prop
erties. In particular, these compounds are valuable in
the control of common insect pests. By the term “insect”
Ur
we do not intend to be limited to the narrow technical
28M
usage of this term to include only six-legged pests but
28MB
intend the broader more common usage which includes
spiders, mites, ticks, caterpillars, nematodes and the like.
In the following described tests demonstrating the util
ity of our new compounds, four insect species represent
ing four insect orders were used. These species are:
( 1) American cockroach—-Periplanela arnericana—-Or
thoptera (designated AR)
(2) Confused ?our beetle—Trib0lium confusum-Cole
optera (designated CFB)
(3) House ?y—-Musca domestica-Diptera (designated
HF)
(4) Spotted milkweed bug—0ncopelms fasciatus—I-Ieter
optera (designated MWB)
In conducting the tests, the compounds are made up
10
10
From these data it can be seen that these new com
pounds are valuable insecticides. Although the speci?c
examples show the use of aqueous solutions of these
compounds as insecticides, they may also be used in the
into solutions, normally 0.1% concentration, using “wet 75 form of emulsions, non-aqueous solutions, wettable pow
3,070,498
5
110. The compound represented by the formula
ders, vapors, and dusts as may be best ?tted to the con
ditions of use.
NCaE»;
The concentration normally used for initial testing is a
0.1% solution. As noted above, however, many of these
(CzHsO)zP(O)—-S—S-O
0 03117
new compounds are effective pesticides at much lower
levels, as low as 0.000l% in some instances.
11. The compound represented by the formula
Since the
e?ective concentration may vary with each compound
and each pest to which it is applied, a general numerical
(CHSOMP (O)—S-——S—C
range of concentrations cannot be stated. It is well with
¢NC3H7
O C3H1
in the skill of the art, however, to determine the effective 10
concentration necessary to kill a signi?cant proportion
12. A process for controlling pests comprising apply
of a speci?c pest or combination of pests under certain
ing thereto an elfective concentration of a compound
conditions of application.
represented by the formula
The foregoing description is given for clearness of un
derstanding only and no unnecessary limitations should be 15
understood therefrom as modi?cation will be obvious to
those skilled in the art.
We claim:
wherein R1 and R2 are alkyl radicals, R3 and R4 are mem
bers of the class consisting of lower alkyl, phenyl and
1. Compounds having the formula
20 substituted phenyl radicals and X is a member of the class
consisting of oxygen and sulfur.
13. A process for controlling pests comprising apply
R20
ing thereto an effective concentration of the compound
XR4
claim 2.
wherein R1 and R2 are alkyl radicals, R3 and R4 are 25 of 14.
A process for controlling pests
members of the class consisting of lower alkyl, phenyl
ing thereto an e?ective concentration
and substituted phenyl radicals and X is a member of the
of claim 3.
class consisting of oxygen and sulfur.
15. A process for controlling pests
2. The compound represented by formula
ing
thereto an effective concentration
30
of claim 4.
16. A process for controlling pests
ing thereto ‘an effective concentration
comprising apply
of the compound
comprising apply
of the compound
comprising apply
of the compound
of claim 5.
3. The compound represented by the formula
(ClH50):P(O)-S—S—C
NCuH4C1
%
OCZH;
. The compound represented by the formula
NCoHi
(C:HsO):P(0)—S-S—C
0 CH:
5. The compound represented by the formula
NGoHs
.
35
%
(C?HltO)2P(O)-S—S—0
O C3H7
6. The compound represented by the formula
of claim 6.
18. A process for controlling pests comprising apply
ing thereto an effective concentration
40 of claim 7.
19. A process for controlling pests
ing thereto an effective concentration
of claim 8.
20. A process for controlling pests
45 ing thereto an elfective concentration
of claim 9.
p 21. A process for controlling pests
ing thereto an effective concentration
of claim 10.
22. A process for controlling pests
60
ing thereto an effective concentration
of claim 11.
formula
(C2H50)IP (O)—-S—S—C
OCzHI
55
. The compound represented by the formula
NCgH:
(CQH50)2P(O)-S—S—G
NClH?
(C2HsO)2P (O)—S—-S—C
OCH:
comprising apply
of the compound
comprising apply
of the compound
comprising apply
of the compound
R‘O\(u’P~S—S-—-C=N.Ra
XR4
and substituted phenyl radicals and X is a member of the
class consisting of oxygen and sulfur, which comprises
reacting substantially stoichiometric quantities of a com
pound having the formula
65
Rio
P(O)SY
O CzHs
%
of the compound
'
R20
8. The compound represented by the formula
. The compound represented by the formula
comprising apply
wherein R1 and R2 are alkyl radicals, R3 and R4 are
60 members of the class consisting of lower alkyl, phenyl
0 C211;
Noni,
%
of the compound
23. A process for preparing compounds having the
N C4Hu
(CzHsOhP (O)——S—S—-C
17. A process for controlling pests comprising apply
ing thereto an etfective concentration of the compound
R20
wherein Y is a halogen atom with a compound having
70 the formula R3NHC(S)XR4 in the presence of a hydro
gen halide acceptor.
No references cited.
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