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Патент USA US3071604

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United grates
ice
ll
B?il?hi
Patented Jan. 1, 1&63
2
‘ cg. are the 3—chloro- or 3-benzene or -toluene sulfony1_
3,071,594
hydroxy-trimethylene sul?de (sulfoxide or sulfon) this
reaction may be shown in the following equation:
THIUPHGSPHORH€ ACID ESTERS AND PROCESSES
F9111 THEER PRDDUCTIUN
Edgar Enders, Leverkusen, and Giinter Unterstenhiifer,
Upiaden, Germany, assignors to Farhenfabrilren Bayer
Aiitiengeseilschaft, Leverkusen, Germany, a corpora
tion of Germany
No Drawing. Filed July 19, 1961, Ser. No. 125,078
Claims priority, application Germany .iuly 23, 1960
16‘ Claims. (Cl. 26(}—327)
The present invention relates to and has as its objects
new and useful thiophosphoric acid esters with insecticidal
properties and processes for the preparation thereof. The
new compounds of this invention may be represented by
the following general formula
10
X in these formulae is the same as said above, also R and
n have the above given signi?cance. Me stands for a
salt forming radical such as an alkali metal, an am
15 monium group and the like, and Tos stands for the p
toluene-sulfonyl-hydroxy group.
Also this reaction suitably is carried out in the presence
of inert organic solvents.
At last the inventive sulioxido or sulfono compounds
in which X and Y are oxygen or sulfur at least one of 20 may be prepared by oxidizing the corresponding sul?do
them being sulfur, R stands for a lower alkyl radical espe
compounds by conventional methods. Thus, with potas
cially up to 4 cmbon atoms and n is a whole number up
sium permanganate there are obtained sulfons and with
to 2 or zero.
hydrogen peroxide (in glacial acetic acid.) there are
obtained sulfoxides:
These compounds may be obtained by methods known
in principle.
Thus, 0.0-dialklythiophosphoric acid
25
halides may be reacted with 3-hydroxy-trimethylene-sul
?de (sulfoxide or sulfon) in the presence of an inert
ROY?P-Y-CH?g”S / RO/
(organic) solvent:
30
The symbols in these formulae have the above given
signi?cance. Suitable thiophosphoric acid ester halides
are chlorides or bromides of 0.0-dimethyl-, diethyl-, diiso
moi/‘RodiP——Y—-CH£32S=O
35
RO/
0H2
\Cég X31110;
Rodi £52 a0
P4435.CH2/s\0
R0
propyl-, O-methyl-O-ethyl-, the 0.0-cyclodimethylene
X, Y and R are the same as said above.
.thiop‘nosphoric acid and the like. Acid-binding agents
effectively kill insects like ?ies, mites, aphids, etc. They
distinguish themselves especially by a good contact
are especially those which simultaneously can act as
The new compounds of the present invention very
solvents such as pyridine, dimethylaniline, triethylam-ine,
insecticidal activity and at the same time by an activity
dimethylbenzylamine and the like. Further inert sol 40 on eating insects such as caterpillars. The compounds
vents are e.g. alcohols, ketones, benzene and the like.
ther acid‘binding agents suitable for the inventive reac
tions are potassium or sodium carbonates or hydroxides
may be used in the same manner as other known phos
phoric acid insecticides, i.e. in a concentration from about
0.0000l% to about 1%, diluted or extended with suit_
or alcoholates, magnesium oxide, zincoxide and the like. 45 able solid or liquid carriers or diluents. Examples of
The inventive esters of the aforeshown type alter
such solid carriers are talc, chalk, bentonite, clay and
native'ly can be prepared by reacting the above mentioned
the like, as liquid carriers there may be used water (if
3~hydroxy-trimethylene-sul?de (sulfon, sulfoxide) with
necessary with commercial emulsi?ers), alcohols, espe
suitable GO-dialkylphosphorus acid halides and subse
cially lower alcohols such as methanol or ethanol, ke—
tones, especially lower ketones such as acetone or methyl
ethyl ketone, liquid hydrocarbons and the like. The new
compounds may furthermore be used in combination with
each other or with known insecticides, fertilizers etc.
As an example for the special utility of the inventive
compounds the ester of the following formula
The symbols again have the above given signi?cance.
Thiol- and thionothiolphosphoric acid esters of the 60 has been tested against caterpillars, flies and aphids.
inventive type are obtained by reacting suitable salts of
Aqueous concentrations of the aforementioned compound
0.0-dialkyl-thiol (or thionothioll) phosphoric acids with
have been prepared by admixing them with the same
trimethylene-sul?des (sulfoxides or sulfons) having in
amount of an auxiliary solvent (acetone). A commercial
3-position an anionic reactive group. Such compounds
emulsi?er (benzyl hydroxy diphcnyl polyglycol ether)
3,071,594
4
3
To a solution of 30 parts by weight of 3-hydroxy-tri
methylene sul?de in 40 parts by volume of pyridine and
is added in an amount of 20% referred to active in
gredient. This premixture then is diluted with water to
the desired concentration. The tests have been carried
40 parts by volume of chloroformic acid there are added
(a) Against caterpillars: White cabbage has been
dropwise at 5—10‘° C. 55 parts by Weight of dirnethyl
thionophosphoric acid chloride. This mixture is stirred
sprayed drip wet with aqueous emulsions as prepared
for 2 hours at 20° C. and then worked up as described in
out as follows:
above in the concentration as indicated below.
Example 1. The compound is decomposed at tempera
tures above 100° C. For purposes of analysis solvents
Cater
pillars (Plutella maculipelmis), 10 each, have been placed
were separated in high vacuum at 90° C.
on the sprayed leaves of the White cabbage; the living
Analysis.—-C5H11O3S2P [214.24].——Calculated: P,
status of the caterpillars has been determined after 24 10
14.45%. ‘Found: P, 14.6%.
hours and 48 hours. The results have been obtained as
Caterpillars are killed completely with 0.002% solu
follows: caterpillars were killed completely with 0.002%
tions. Flies are killed completely with 0.02% solutions.
solutions.
‘
Aphids are killed to 95% with 0.02% solutions. Spider
(b) Against ?ies (Drosophila): About 50 ?ies are
placed under covered Petri dishes in which drip wet ?lter 15 mites are killed to 50 with 02% solutions (resistant).
Systemic action with 0.004% solutions=l00%.
paper has been placed which were sprayed with an in
secticidal solution of a concentration as shown below.
Example 3
The living status of the ?ies has been determined after
CQH?O
24 hours. The following results have been obtained: flies
20
were killed completely with 0.002% solutions.
(0) Against aphids (Mycus persicae): Heavily infested
bean plants (Vicia faba) have been sprayed drip wet with
S
\ll
-
CH1
/ \
P-S ——CE /S
CaHsO
CH2
solutions as prepared above. The effect has been deter
mined by evaluation after 24 hours by counting the dead
To a solution of 23 parts by weight of the potassium
salt of 0.0-diethyl-dithiophosphoric acid ester in 200 parts
pests either on the surface of the soil or still remaining
by volume of acetone there are added 22 parts by weight
on the plants. The following results have been obtained:
aphids were killed completely with 0.02% solutions.
The following examples are given to illustrate the pres
of the potassium salt of 3-hydroxy-trimethylene sul?de-O
sulfonic acid and this mixture is heated under re?ux.
Thereafter the solvent is distilled off, the residue is mixed
with water and the benzene is extracted. The benzenic
ent invention.
30 solution is dried over calcium chloride and concentrated
Example 1
in vacuum.
The remaining oily 0.0~diethyl-S-(3-thia
cyclobutlyl)-dithiophosphoric acid ester is freed from vola
tile ingredients in high vacuum at 80° C.
Caterpillars are killed completely with 0.1% solutions.
C 21150
To a solution of 30 parts by weight of 3-hydroxy-tri 35 *lies and aphids are killed completely with 0.01% solu
tions. Spider mites are killed completely with 0.01%
methylene sul?de in 40 parts by volume of pyridine and
solutions (resistant). Systemic action with 0.1% solu
40 parts by volume of chlcroformic acid there are added
dropwise at 5—10° C. 64 parts by weight of diethyl
tions=100%.
diluted hydrochloric acid.
the ‘following compound
By the same way, with 0.0-diethyl-thiolphosphoric acid
thionophosphoric acid chloride. This mixture is stirred 40
potassium salt there is obtained in an analogous manner
for 2 hours at 20° C. and poured into ice-water and
Thereafter there are further
added 200 parts by volume of benzene, the organic layer
centP—-S —C%asS
is separated, washed with water and dried over calcium
chloride. The thiophosphoric acid ester obtained is puri
?ed by vfractionated distillation. B.P. 125—135° C./0.6
mm. Hg; nD2°-4: 1.5080.
Analysis.-—~C-;H15O3S2P
[242.3] .——Calculated:
26.4%; P, 12.8%. Found: S, 25.3%; P, 13.55%.
021350
Cég
Example 4
S!
021150
Caterpillars and ?ies are killed completely with
0.002% solutions. Aphids are killed completely with
0.02% solutions. Spider mites are killed completely with
0.2% solutions (resistant). Systemic action on aphids
C2H5O
0
\ ll
CH2
/ \
/P—'O—Cg CH2/S
To a solution of 30 parts by weight of S-hydroxy-tri
methylene sul?de in 40 parts by volume of pyridine and
60 parts by volume of toluene there are added dropwise
47 parts by weight of phosphoric acid diethylester-mono
(Doralis fabae) with 0.0008% solutions=90%.
By oxidizing the above ester with about the calculated
amount (small excess) of potassium permanganate in ‘
aqueous solutions in the presence of a small amount of
chloride in 100 parts by volume of toluene at a tempera
ture of 15~20° C. while- passing over nitrogen. After ?n
ishing of the reaction there are added in several propor
acetone at low temperatures (about 5° C.) there is ob~
tions at a temperature of 30° C. 9.6 parts by weight of
tained the corresponding sulfon
sulfur and this mixture at last is warmed for 15 minutes
60 to 70° C. After cooling down the mixture is poured into
ice-water and diluted hydrochloric acid, the organic layer
is washed twice with water, dried over calcium chloride
and the toluene is distilled off in vacuum. There is ob
tained as an oily residue the 0.0-diethyl-O-(3-thiacyclo
With hydrogen peroxide in glacial acetic acid ‘at about
room temperature there is obtained the corresponding
butyD-thiophosphoric acid ester.
We claim:
1. A compound of the formula
sulfoxide
R-O
X
CH
70
in which R stands for alkyl of 1 to 4 carbon atoms, X
and Y are members selected from the group consisting
75 of oxygen and sulfur, one of them being sulfur, and n
3,071,594
5
6
stands for a number selected from the group consisting
6. The compound of the following formula
of zero, one and two.
02H“)
2. The compound of the following formula
C2Ha0\?
/C§z
5
' 021150
CH2
011150
CH2 /0
/
10
CH2
5 Th
'
°
s=o
_
f
1
)352
20
01%
_
UNITED STATES PATENTS
2,882,278
McConnell etal. ______ __ Apr. 14, 1959
2,939,871
Pyne et al. ____________ __ June 7, 1960
1,082,915
Germany ____________ __ June 9. 1960
/P-'O—OE /s
01130
_
References Cited 1n the ?le of th1s patent
6 ° owmg ‘mm a
0H30\|s|
'
.
\c?z
d f th f H
e compo“
10. A compound of claim 1 wherein X is oxygen and
Y is sulfur
/ \
02135 O/
CH:
sulfur.
15
P—-O—CH
U2H5O
is oxygen.
9. A compound of claim 1 wherein X and Y are each
4. The compound of the following formula
\Il
0H:
8. A compound of claim 1 wherein X is sulfur and Y
\ / \
CH2 0
“H50 S
0
\il-s-oé >8
P—O-—C£ \s/
C2350
CH,
7. The compound of the following formula
3. The compound of the following formula
C9H5O S
/ \
P-S-CH /s
P"'O_C€ /S
021150
3
\II
FOREIGN PATENTS
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