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Патент USA US3030275

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‘*1
"C
ate
3,030,265
Patented Apr. 17, 1962
2
1
The new compounds of this invention may be readily
prepared by reacting a metal or ammonium salt con
5,030,265
BUTYNYL PHGSE‘HATES
taining the desired Z radical with the reaction product of
Joseph ‘W. Baker ‘and John P. Chupp, Kirlrwood, Mo.,
assignors to Monsanto Chemical Company, St. Louis,
a dihalogenated butyne and a salt of a phosphoric acid.
The proportions of the reactants will vary in accordance
Mo. a corporation of Delaware
with the particular product to be obtained. The reaction
of the Z radical salt, the butyne and the acid salt may
No Drawing. Filed Nov. 9. 1959, Ser. No. 851,501
15 Claims. (Cl. 167--22)
also be carried out in situ.
This invention will be more fully understood by ref
This invention relates to'new organic phosphorus com
pounds and to insecticidal formulations comprising such 10 erence to the following examples. These examples, how
ever, are given for the purpose of illustration only and
compounds. More particularly, the invention is con
are not to be construed as limiting the scope of the pres
cerned with those phosphorus compounds which are de
ent invention in any way.
rived from the interaction of a metal or ammonium salt
and a halogenated butynyl salt of phosphoric acid.
EXAMPLE I
It is an object of this invention to provide new and 15
0,0-Diethyl S-(4-Thiocyanato-Z-Butynyl)
Phosphorothiolate
useful compounds of phosphorus. It is a further object
of this invention to provide a new class of highly useful
insecticides. Still a further object is to provide new and
useful formulations comprising such insecticides.
The compounds of the present invention are phosphorus 20
derivatives of the general formula:
no X
A suitable reactor was charged with 7.6 grams (0.10
\I!
mole) of ammonium thiocyanate dissolved in 100 ml. of,
PX’CHzCECCHuZ
R’O/
'25
wherein R and R’ represent like or unlike lower alkyl
radicals or alkoxy substituted lower alkyl radicals, and X
acetone. There was added 20.0 grams (0.078 mole) of
S-(4-chloro-2-butynyl) 0,0-diethyl phosphorothiolate
with stirring. The mixture was heated at refluxing tem
perature for 4 hours, after which it was cooled and
and X’ are oxygen or sulfur. As employed herein, the
?ltered. The ?ltrate was stripped of acetone under vac
term “lower” connotes radicals having from 1 to about 4
uum and water was added. There was then added 100
30
carbon atoms. In said general formula, Z represents a
ml. of methylene chloride, and an aqueous layer sepa
radical selected from cyano (--CN), thiocyano (—SCN),
rated; The non-aqueous layer was washed with water and
alkoxy (—OR"), sul?de (—SR"), mono or dithiocar
then stripped under ‘vacuum to 100° C. at 10 mm. pres
bamate
sure to remove the methylene chloride. A yield of 15.3
S
35 grams (70.5% of theory) of 0,0-diethyl S-(4-thiocy
H
ll
[I
anato-2-butynyl) phosphorothiolate was obtained. Anal
ysis showed 10.6% phosphorus and 22.1% sulfur as com
(—S CNRZ", -s CNRg", or —0 CNRz”)
xanthate
pared with calculated values of 11.1% phosphorus and
s
l!
;
22.9% sulfur.
(—- s o o R”)
40
benzothiazo
-
-
When 23.4 grams (0.078 mole) of S-(4-chloro-2
butynyl) 0,0-dimethoxyethyl phosphorothiolate is sub
stituted for the phosphorothiolate in the above charge,
there is obtained 0,0~dimethoxyethyl S-(4-thiocyanato-2
butynyl) phosphorothiolate in good yield.
L \.
phthalimido, succinirnido and saccharinyl wherein R" is
EXAMPLE II
45
4-(Diethoxyphosphinothioyllhio)-2-Butynyl
Diethyldithiocarbamate
an acyclic radical containing from 1 to about 8 carbon
atoms or a phenyl radical. As employed in this applica
tion, the term “saccharinyl” designates the radical derived
021150
from saccharin by removal of the hydrogen from the 50
nitrogen atom.
'
'
s
s
\lll’sCHaCiCCHisgN/
C2H5O
Exemplary of the radicals represented by R” are the
C 21515
0211s
A suitable reactor was charged with 9.12 grams (0.125
mole) of diethylamine and 70 ml. of acetone. There was
alkyls such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
tertiary butyl, isoamyl, n-hexyl,‘ Z-methyl-l-pentyl, n
4.56 grams (0.06 mole) of carbon disul?de at '
heptyl, 3-ethyl-2-pentyl, n-octyl, 2-ethylhexyl, etc.; the 55 added
5-25”
C.
The mixture was stirred for one hour at 25
alkenyls and alkynyls such as vinyl,_allyl, n-butenyl-Z,
30° C., after which 15.0 grams (0.058 mole) of S-(4
diisobutenyl, propynyl, 2-butynyl, 3-hexynyl, etc.; other
chloro-Z-butynyl) 0,0-diethyl phosphorodithioate was
acyclics such as methoxyethyl, ethoxyethyl, , 2-chloro
added. After heating for 5 hours at 65—70° C., the re
ethyl, 2-chloroallyl, benzyl, etc.; and phenyl radicals such
sultant
mixture was cooled and ?ltered. The ?ltrate was
as phenyl, xenyl, tolyl, chlorophenyl, nitrophenyl, cyano 60
stripped of acetone, and diethyl ether was added. After
phenyl, methoxyphenyl, etc.
washing with water and stripping to 75 ° C. at 5 mm. of
Included within the above general structural formula
pressure,
a yield of 17.8 grams of 4-(diethoxyphosphino
is a preferred group of compounds which have the
thioylthio) -2-butynyl diethyldithiocarbamate was ob
formula:
ROX
65
R’O
1
tained
EXAMPLE III
0,0-Diethyl S-(4-n-Pentylthi0) -2-Butynyl
Phosphorodithioate
where R and R’ are like or unlike lower alkyl radicals,
and X and R" have the same meaning as above. Such 70
C2H5O
against a wide variety of pests. I
C2H5O
compounds display an optimum degree of biocidal activity
->
S
PSCHzCEC CHzSCrHn
3,030,266
1%
EXAMPLE VII
A'suitable reactor was charged with 12.3 grams (0.1
mole) of 1,4-dichl0robutyne-2 and 20.3 grams (0.1
0,0-Diethyl S-(4-Berzz0thiaz0lethz'o)LZ-Butynyl
mole) of ammonium 0,0-diethyl phosphorodithioate in
Phosphorodithioate
200 ml. of acetone. .After heating at re?uxing tempera
ture for 2 hours,~the mixture was cooled, and there was
added 5.3 grams (0.05 mole) of sodium carbonate fol
.
C2H5O
lowed by 10.4 grams (0.1 mole) of amyl mercaptan. The
The
\
S
/
A suitable reactor was charged with 20.3 grams (0.1
residue .was extracted with methylene chloride and washed 10
mole) of ammonium 0,0-diethyl phosphorodithioate in
with water. The remaining solution was stripped to 80”
C. at 3 mm. pressureto yield 23.2 grams (68% of theory)
200 ml..of acetone and 12.3 grams (0.1m01e) of 1,4
dichlorobutyne~2. _ The mixture was heated at re?uxing
of 0,0-diethyl S-(4~n-pentylthio)-2-butynyl phosphorodi
thioate as an amber liquid.
PSCH2CECOH2SC/ l 1
022150
resultant mixture was heated at re?uxing temperature for
14 hours after which it was stripped of acetone.
N
S
temperature for 2 hours and was then cooled.
There
15 was added 16.7 grams (0.1 mole) .of mercaptobenzothia
EXAMPLE IV
zole followed by 6.2 grams (0.06 mole) of sodium car
0,0-Dz'ethyl S-(4-Thiocyanato-2~Butynyl)
Phosphorodithioate
bonate. This latter mixture was heated at re?uxing tem
perature for 2.0 hours after which the solids were ?ltered
out, and the ?ltrate was stripped of acetone. The resi
20 due was extracted with methylene chloride, and the or
ganic solution was washed with water and stripped to
olmo 0
\ll
_
PSCHzCzCCHzSCN
021150
120° C. at 5 mm. of pressure. There was obtained 26.0
.
A suitable reactor was charged with dichloride and am
monium salt as in Example III. After cooling, 8.1 grams
grams (65% of theory) of 0,0-diethyl S-(4-benzothia
‘16.3 grams 'of 0,0-diethyl S-(4-thiocyanato-2-butynyl)
thioate.
zo1ethi0)-2-butynyl phosphorodithioate as an amber
.,(0.1 mole) of sodium thiocyanate was added, and the 25 liquid.
When the mercaptan is 20.2 grams (0.1 mole) of 6
.resultant mixture'was heated at re?uxing temperature for
chloromercaptobenzothiazole, and the second re?ux heat—
- 15 hours. The reaction product was stripped of acetone,
'ing is shortened to 10 hours, the yield is 28 grams (92% of
extracted with methylene chloride, and then stripped again
theory) of the 6-chloro derivative of the phosphorodi
to 98° C. at 10 mm. of pressure. There was obtained
phosphorodithioate.
vIn order‘ to obtain 0,0-dietl1yl S-(4-benzothiazolethio)
' Z-butynyl phosphorothiolate, 18.7 ‘grams (0.1 mole) of
EXAMPLE V
ammonium 0,0-diethyl phosphorothioate was substituted
0,0-Diethyl ‘S-(p-Chlorophenyl) Thio-Z-‘Butynyl
Phosphorothiolate
O
v
/
as an amber liquid.
‘
V
.
EXAMPLE VIII
.
‘l
\rsoHm-Eo
oms<
-
for the dithioate in the charge. The yield was 21.3 grams
\
>>>-o1
0,0—Diethyl S-(4-Allylthz'o) -2-Butynyl Phosphorothiolate
——
021-150
Asuitable reactor was charged with 18.7 grams (0.1 40
mole) of ammonium 0,0-diethyl phosphorothioate in
200 ml. ofacetone and‘ 12.3 grams (0.1 mole) of 1,4
dichlorobutyne-2. After heating at re?uxing temperature
for 2 hours, the mixture was cooled, and 6.2 grams (0.06
mole) of sodium carbonate was added followed immedi
C2H50\(?PSCH2CECCH2SCH2CH=GH2
7' CZH5O
A suitable reactor was charged with 3.7 vgrams (0.05
mole) of allyl mercaptan in 100 ml. of ethanol and placed
ately by 14.7 grams (0.1 mole) of p-chlorothiophenol.
under a nitrogen atmosphere. There was slowly added
2.7 grams (0.05 mole) of sodium methylate. This mix
The resultant mixture‘was heated at re?uxing temperature
ture was stirred at room temperature for 1 hour, after
The residue was extracted with methylene chloride, and '
which 12.8 grams (0.05 mole) of S-(4-chloro-2-butynyl)
0,0-diethyl phosphorothiolate was added. The resultant
the organic extract was washed with water and stripped
to 120° C. at 5 mm. of pressure. A yield of 30.7 grams
mixture was heated at re?uxing temperature for 3 hours,
the alcohol then being removed under vacuum. The res
(84% of theory) of 0,0-diethyl S-(p-chlorophenyl)thio
.idue was extracted with methylene chloride, washed with
for 13 hours after ‘which the acetone was stripped o?.
dilute sodium carbonate solution and water, and ?nally
2-butynyl phosphorothiolate was obtained.
stripped to 110° C. at '1 mm. of pressure. There was
When 20.3 grams (0.‘1rnole) of ammonium 0,0-diethyl
phosphorodithioate was substituted for the phosphorothi 55 obtained 10.2 grams (71% of theory) of 0,0-diethyl S
.(4-allythio) -2-butyny1 phosphorothiolate.
oate, a yieldof 36.8 grams (97% of theory) of 0,0-di
When 13.6 grams (0.05 mole) of S-(4-chloro-2-butynyl)
ethyl S-(p-chlorophenyl)thio-2-butynyl phosphorodithio
0,0¢diethy1 phosphorodithioate'was substituted for the
rate was obtained.
‘EXAMPLE VI
0,0-Diethyl S-(4-n-Pentylthi0)<2~Butynyl
Phosphorothiolate
021150
0
\u
_
PSOHZC=OCIIZSC5HH
021150
phosphorothiolate, a yield of 7.1 grams of 0,0-diethyl
60 S-(4-ally1thio)-2-butyny1phosphorodithioate was obtained
as an amber liquid.
EXAMPLE IX
0,0-Diethyl S-(4-Ethylthio) -2-Butynyl Phosphorothiolate
CsHa'O 0
Fsornozccmscun
In the procedure of Example IV, 15.6 grams (0.15
Q mole) of amyl mercaptan was substituted for the chloro
thiophenol, and the secondre?ux heating was continued,
for an additional hour. The yield'was 32.0 grams (100%
021150
'
Following the procedure of Example VIII, 3.1 grams
(0.05 mole) of ethyl mercaptan was substituted for the
of theory) of 0,0-diethyl S-(‘4-n-pentylthi0)-2-butynyl 70 allyl
mercaptan. The yield was 10.4 grams (75% of
phosphorothiolate.
.
theory)
of 0,0-diethyl S-(4-ethylthio)~2-butynyl phos
When 12.2 grams (0.15 mole) of thiophenol was sub
phorothiolate.
Analysis showed 10.2% vphosphorus and
stituted for the mercaptan, a yield of 25 grams (72% of
theory) of 0,0-diethy1 S-(4-phenylthio)-2-butynyl phos
phorothiolate was obtained.
.
23.2% sulfur'as opposed to calculated values of 11.2%
phosphorus and 23.0% sulfur.
3,030,265
6
5
EXAMPLE XIV
In the same manner, using 13.6 grams (0.05 mole) of
0,0-Diisopr0pyl S-(4-Ethoxythi0carb0nylthio-Z-Butynyi)
S-(4-chloro-2-butynyl) 0,0-diethyl phosphorodithioate in
stead of the phosphorothiolate, a yield of 4.0 grams
T. '
I
of 0,0-diethyl S-(4-ethylthio)-2-butynyl phosphorodithio
ate was obtained as an amber liquid.
(0119201110 0
'
EXAMPLE X
s
(CI-Is)2CHO
A ‘suitable reactor was charged with 28.5 grams (0.1
0,0-Diis0pr0pyl S-(4-Ethylthio) -2-Butynyl
Phosphorothiolate
(C H3) 2 C H O
Phosphorothiolate
mole) of S-(4-chloro-2-butynyl) 0,0-diisopropyl phos
10 phorothiolate in 200 ml. of acetone, and 16.0 grams (0.1
mole.) of solid potassium ethylxanthate. The mixture
O
P SCHzCEC CH2SC2H5
was heated at re?uxing temperature for 12 hours and
was then cooled and ?ltered. The ?ltrate was stripped
Again following the procedure of Example VII, the
of acetone, and the residue was‘extracted with methylene
reactants were 2.5 grams (0.04 mole) of ethyl mercaptan, v 15 chloride. The extract was washed with water and stripped
(0 Hz) 2 C H 0
100 ml. of ethanol, 2.2 grams ‘(0.04 mole) of sodium
to 110° C. at 1 mm. of pressure
methylate, and 11.4 grams (0.04 mole) of S-(4-chloro
Z-butynyl) 0,0-diisopropyl phosphorothiolate. Heating
"I
There was obtained
0,0-diisopropyl S~(4aethoxythiocarbonylthio-Z-butynyl)
at re?uxing temperature was carried out for 4 hours, and
the ?nal stripping was to 120° C. at 1 mm. of pressure. 20
phosphorothiolate as an amber liquid.
EXAMPLE XV
A yield of 9.4 grams (76% of theory) of 0,0-diisopropyl
S-(4-ethylthio)-2-butynyl phosphorothiate was obtained.
N-(4-Diethoxyphosphinothioylthio-2~Butyny'l) v
Phthalimide
EXAMPLE XI
0,0-Diethyl S-(4-Cyan0-2-Butynyl) Phosphorodithioate
25
C2H5O\?PSCHzCECCHzCN
021150
021150
Y
A suitable reactor was charged with 2.5 grams (0.05 30
mole) of sodium cyanate, 13.6 grams (0.05 mole) of S
A suitable reactor was charged with 10.9 grams (0.04
mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphoro
dithioate, 7.4 grams (0.04 mole) of potassium phthalimide,
(4-chloro-2-butynyl) 0,0-diethyl phosphorodithioate, and
and 150 ml. of acetone. After heating this mixture at
refluxing temperature for 8 hours, it was cooled and ?l
35 tered. The ?ltrate was stripped of solvent. The residue
the manner of Example IV to yield 0,0-diethyl S-(4
was extracted with methylene chloride, washed with water,
cyano-Z-butynyl) phosphorodithioate.
and stripped to 80° C. at 1 mm. of pressure. A' yield of
7.5 grams of N-(4-diethoxyphosphinothioylthio-Z-butynyl)
EXAMPLE XII
100 ml. of acetone. The mixture is heated at re?uxing
temperature for a period of 8 hours, and worked up in
0,0-Diethyl S- [4- (3-0x0-1,Z-Benzisothiazolin-Z-yl) -2
phthalimide was obtained as a dark viscous oil.
40
The speci?c activity of some of the individual com
pounds disclosed herein is enumerated below. At the
outset it should be made clear that such data is merely
exemplary, and that similar results are obtained by em
ploying any of the other compounds within the scope
of this invention. Tests of systemic activity were made
45
by immersing the excised stems of bean plants in diluted
emulsions of the compounds for three days. Leaves were
thenlexcised, infested with the selected pest, and the per
A suitable reactor was charged with 12.9 grams (0.05
cent kill was noted after 48 hours. Tested against the
mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphoro
thiolate, 10.2 grams (0.05 mole) of sodium saccharin 50 two-spotted spider mite, emulsions containing 100 p.p.m.
of the ?rst compound of Example V or the ?rst compound
and 100 ml. of acetone. The mixture was heated at re
of Example'VI killed 100% of the test organisms. A
?uxing temperature for 12 hours, followed by cooling and
kill of 90% was achieved using the third compound of
?ltration. The ?ltrate was stripped of acetone. The res
Example VII. Systemic tests against the bean beetle
idue was then extracted with methylene chloride, washed
with water, and stripped to 110° C. at 1 mm. of pressure. 55 showed 100% kill at a concentration of 0.004% of the
There was obtained 11.0 grams (61% of theory) of 0,0
diethyl S- [4-( 3-oxo-1,2-benzisothiazolin-‘2-yl) -2-butynyl]
phosphorothiolate, dioxide.
EXAMPLE XIII
0,0-Diethyl S-(4-Meth0xy-2-Butynyl) Phosphorodithioate
?rst compound of Example I and 60% kill at 0.004% of
the ?rst compound of Example VI.
The insecticidal e?ectiveness of the new compounds
was also demonstrated in contact tests on the mobile and
60 resting stages, as well as on the ova, of the two-spotted
spider mite. Concentrations of 0.1% resulted in 100%
kill using any of the following: the ?rst compound of
Example I; the compound of Example IV; either com
pound of Example V; the ?rst compound of Example VI;
65 and either of the ?rst and third compounds of Example
CzHsO
A suitable reactor was charged with 11.0 grams (0.04
VII.
Further, at concentrations of 0.05% either com
mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphorodi
pound of Example V still gave 100% kill against the
thioate, 2.2 grams (0.04 mole) of sodium methylate, and
mobile stage.
100 ml. of methanol.
The mixture was heated at re?ux
.
Using the compounds of this invention against yellow
ing temperature for 3 hours, after which it was ?ltered. 70 fever mosquito larvae, concentrations of 0.001% of the
active ‘ingredient gave 100% kill with any one of the
The ?ltrate was stripped of solvent, and the residue was
compounds of Examples II through V. At 0.0003%,
extracted with methylene chloride and Washed with water.
Stripping to 100° C. at 1 mm. of pressure yielded 7.4
grams (69% of theory) of 0,0-diethyl S-(4-methoxy-2
butynyl) phosphorodithioate.
-
100% kill resulted by using the ?rst compound of Ex
ample VI, while the ?rst cornpound, of Example I gave
100% kill even with the concentration reduced to
3,030,265
‘diluent or carrier. Althoughit is not intended that this
invention be limited‘to any‘speci?c proportions of active
ingredient and ‘adjuvant,.it should be noted that ready
to'use liquid formulations comprising from about 0.001
to 5% of the active ingredient based upon the weight of
the formulation ‘are preferred. In such liquid formula
tions it is also preferred that the 'adjuvant comprise less
0.00002%. The ?rstcompound ofExarnple I was also
tested for residual action on ?lter paper. Against the
red ?our beetle, kills of 100% and 90% were obtained
with concentrations of 1.0% and 0.5% respectively.
It will be understood that the terms “insect” and “in
secticide” are used herein in theirbroad common usage to
include spiders, mites, ticks, and like pests which are not
in the strict biological sense classed as insects. Thus,
than about 5% ‘based upon the weight .of the formulation.
With ready to use solid formulations, the parts of con
the usage herein conforms to the de?nitions provided by
Congress in PubliciLaw 104, the “Federal Insecticide, I10 centrate and diluent or carrier are substantially the same
as de?ned for the liquids. However, in such solid formu~
Fungicide, and Rodenticide Act” of 1947, section 2, sub
lations, the use of from about 2.5 to 25% of the active
ingredient based upon the weight of the formulation is
preferred. The percentage of 'adjuvant preferred in the
solids is substantially the same as in the liquid formula
tions.
Itis also intended that the term “adjuvant” ‘includes
.solid carriers of the type of pyrophyllite, talc, clay di
atomaceous earth, and the like; and various mineral pow
section h, wherein the term “insect” is used to refer not
only to those small invertebrate animals belonging mostly
to the class Insecta, comprising six-legged,‘ usually winged
forms, as beetles, bugs, bees, flies, and so forth, but also
to their allied classes of arthropods whose members 'are
Wingless and usually have more than sixlegs, ‘as spiders,
mites, ticks, centipedes, and wood lice.
For maximum effectiveness the active ingredients of the
present invention are admixed in:.insecticidally e?ective 20 ders, such 'as calcium sulfate and the like, which act as a
dispersant, as a carrier, and in some instances perform
amount with an insecticidaladjuvant. In order to pro
the-function of a surface-active agent.
vide formulations particularly adapted for ready and‘ ef
Another method of applying'these insecticides is in
ficient application to insects using conventional equipment,
such formulations comprise those of both the liquid and
the form of a water'suspension. However, to obtain an
solid types as Well as the “Aerosol” ‘type formulations. '1 "
Application may be directly to the insects, to the plant
active aqueous suspension, there should be employed ‘a
surface-active agent in sutticient amount to disperse and
suspend the active ingredient. Examples of such surface
active agents which can be employed in forming disper
hosts of such insects, to soil or other media used for grow
ing plants. In the pure state the active ingredients may
be too effective or too potent in some applications to
sions include the soft or hard sodium or potassium soaps,
contact but thoroughly dispersed on the surface “to be
.taurides; the alkylarylpolyether alcohols; the fatty acid
have practical utility. For example, for most ‘effective "30 tall-oil, salts'of the alkyl and alkylaryl sulfonates; alkyl
sulfates; a-lkylamide sulfonates, including fatty methyl
protection, it'is preferred to apply the materialsrin intimate .
esters of .polyhydric alcohols; the ethylene oxide addition
products of such esters; and the addition products of
long-chain mercaptans and ethylene oxide. Still other
surface-active agents can be employed, the above merely
protected. Therefore, the active ingredients have incor~
porated therewith a relatively inert surface-active ‘agent
or adjuvant as a dispersing medium.
Furthermore, such
adjuvants have the effect of requiring only minute quan
showing a representative ‘list of the more common vmate
rials.
tities of said ingredients of some formulations to obtain
effective protection. A further advantage of so extend
It should be pointed out that the formulations of this
invention may also include sticking or adhesive agents,
indicators and other active biocidal ingredients.‘ Such
ing this material is to permit'?eld application by methods
readily employed and still obtain effectively complete
coverage of the material being protected.
Thus, the formulations of thisinvention comprise the
other ingredients may be supplementary insecticides,
fungicides, bacteriocides, nematocides or selective herbi
above de?ned active ingredients and ‘a suitable material
as an adjuvant therefor.
cides.
The important feature ‘of the
While the invention has been speci?cally described with
regard to several embodiments, it is not thereby limited,
invention is to provide an adjuvant such that upon the
preparation of'a formulation of a concentration appropri
and it is to be understood that modi?cations and varia
tions thereof obviousto those skilled in the art may be
made without departing from the spirit or scope of the
ate for any particular application, the adjuvant Will be
present to provide the proper type .of contact with the
material being protected. Thus, in one embodiment the
invention.
adjuvant can comprise a surface-active agent such as a 50
detergent, a soap, or other wetting agent.
What is claimed ‘is:
l. A compound of'the formula
Such a formula
tion then comprises the active ingredient incombination
with a minor proportion of the surface-active agent or
adjuvant.
Such 'a formulation is of practical merit be
cause of its concentrated form and ease of‘transportation, 55
storage, and the like. Such a formulation lends itself
directly to further dilution with a diluent or carrier with
where Rand R’ are selected‘from the group consisting of
out resorting to complicated mixing and blending pro
cedures.
Thus, such a formulation can be further diluted
with a solid carrier of the dust type by a simple mixing
operation. Likewise, such a formulation can be directly
suspended in water or can be further diluted with an oil
lower alkyl and alkoxy substituted lower alkyl radicals,
60
X and X’ are selected from oxygen and sulfur, and Z is
selected from the group consisting of cyano, thiocyano,
phthalimido, 'suc'cinimido, ibenzothiazo, saccharinyl, OR”,
SR",
which upon mixing with water thereby forms .an oil-in
i
i
|
water emulsion containing the active ingredient. One fur- '
SCNRZ”, ooNm”, sdNRi”, and siioR"
ther example of the utility of such a formulation com 65
where R" is‘selected fromalkyl and alkenyl radicals hav
prises the preparation by further dilution with a solid
ing '1 to 8 carbon atoms and'phenyl radicals.
carrier of a Wettable powder which upon admixture with
"2. A compound of the formula
water prior to-application forms a dispersion of the
active ingredient and the solid carrier in water.
R0 X
In the preparation of the above-described concentrates,
PSCH2OECOH2SR"
the active ingredient may comprise up to about 95% 0f
‘R’O
the concentrated formulation. To obtain 100 parts of
already to use liquid formulation, from 1 to 50 parts of
whereR and R’ are ‘lower alkylradicals, X is selected
_.a concentrate-is admixed with from 50 to 99parts of a 75 from oxygen and sulfur, and.R".-is selected fromalkyl
3,030,265
10
X and X’ are selected from oxygen and sulfur, and Z is
selected from the group consisting of cyano, thioc'yano,
and alkenyl radicals having 1 to 8 carbon atoms and
phenyl radicals.
phthalirnido, succinimid-o, benzothiazo, saccharinyl,
3. 0,0-diethyl S-(p-chlorophenyl)thio-Z-butynyl phos
phorothiolate.
OR”, SR",
4. 0,0-diethyl S-(4-ethy1thio)-2-butynyl phosphoro
s
0
thiolate.
siiNRz", OiiNRZ", siiNRy’, and srlion"
thioate.
where R” is selected from alkyl and alkenyl radicals hav
5. 0,0-diethyl S-(4-ethylthio)-2-'butynyl phosphorodi
6. 0,0-diethyl S-(4emethoxy-2-butynyl) phosphoro
10
dithioate.
7. 0,0-diethyl S-(4-thiocyanato~2-butytnyl) phosphoro
ing 1 to 8 carbon atoms and phenyl radicals.
13. A method of combatting insects which comprises
treating the insects externally and the insect habitats
with a composition containing as an essential active in
thiolate.
8. 0,0-diethyl S-(4-allylthio)-2~butynyl phosphorodi
thioate.
9. 0,0 - dimethoxyethyl
S-(4-thiocyanato-2-butynyl)
gredient thereof a compound of the formula
ROX
15
\H
rsornozoornsa"
phosphorothiolate.
10. An insecticidal ‘formulation comprising an insecti
cidal adjuvant and as an essential active ingredient there
of a compound of the formula
BOX
R’O
where R and R’ are lower alkyl radicals, X is selected
20 from oxygen and sulfur, and R" is selected from alkyl
and alkenyl radicals having 1 to 8 carbon atoms and
phenyl radicals.
where R and R’ are selected from the ‘group consisting of
lower alkyl and alkoxy substituted lower alkyl radicals,
14. A method of protecting plants from insects which
comprises treating the plant with a composition contain
25 ing as an essential active ingredient a compound of the
formula
X and X’ are selected from oxygen and sulfur, and Z is
RO\)“(PX'CHaCEOCHzZ
selected from the group consisting of cyano, thiocyano,
phthalimido, succinimido, benzothiazo, saccharinyl, OR”,
SR”,
s
I!
l!
I]
R'O
30
where R and R’ are selected from the group consisting of
ll
SONRZ”, OONRQ”, soNRl", and SCOR"
lower alkyl and \alkoxy substituted lower alkyl radicals,
where R” is selected from alkyl and alkenyl radicals hav
ing 1 to 8 carbon atoms and phenyl radicals.
11. An insecticidal formulation comprising an insecti
cidal adjuvant and as an essential active ingredient there
of a compound of the formula
X and X’ are selected from oxygen and sulfur, and Z is
selected from the group consisting of cyano, thiocyano,
35
phthalimido, succinimido, benzothiazo, saccharinyl,
OR”, SR”,
s
s
siiNRw, Oil/NR2", scliNm", and srlion"
ROX
40 where R” is selected from alkyl and alkenyl radicals hav
R’O
where R and R’ are lower alkyl radicals, X is selected
from oxygen and sulfur, and R" is selected from alkyl
and alkenyl radicals having from 1 to 8 carbon atoms
and phenyl radicals.
12. A method of combatting insects which comprises
treating the insects externally ‘and the insect habitats
ing 1 to 8 carbon atoms and phenyl radicals.
15. A method of protecting plants from insects which
comprises treating the plant with ‘a composition contain
ing as an essential active ingredient a compound of the
45
formula
with a composition containing as an essential active in
gredient thereof a compound of the formula
50
R’O
where R and R’ are selected from the group consisting of 55
lower alkyl and alkoxy substituted lower alkyl radicals,
R’O
where R and R’ are lower alkyl radicals, X is selected
from oxygen and sulfur, and R” is ‘selected from alkyl
and alkenyl radicals having ‘from 1 to 8 carbon atoms
and phenyl radicals.
No references cited.
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