close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3021361

код для вставки
United States Patent 0 r' cc
3,021,351
Patented Feb. 13, 1962
2
1
3 0 02H;
(ID
3,021,351
PHOSPHORUS DERIVATIVES AND PROCESS FOR
THEIR PRODUCTION
Ernst Schegk, Wuppertal-Elberfeld, and Gerhard
Schrader, Wuppertal-Cronenberg, Germany, as
CHa
have been tested against aphids ‘and spider mites. Aque
signors to Farbenfabriken Bayer Aktiengesell
schaft, Leverkusen, Germany, a corporation of
ous solutions of the aforementioned compounds have been
prepared by admixing them with the same amount of an
auxiliary solvent (acetone). A commercial emulsi?er
Germany
No Drawing. Filed Apr. 28, 1960, Ser. No. 25,211
Claims priority, application Germany May 2, 1959
1 1 Claims.
_
(Cl. 260—461)
(benzyl hydroxy diphenyl polyglycol ether) is added in
10 an amount of 20% referred to active ingredient.
This
premixture then is diluted with water to the desired con
centration. The tests have been carried out as follows:
The present invention relates to and has as its objects
(a) against aphids (species Doralis fabae). Heavily in
new and useful insecticidally active compounds and
fested bean plants (Vitia faba) have been sprayed drip
processes for their production. The new compounds of
the present invention are (di)-thiophosphoric, phosphonic 15 wet with solutions as prepared above in a concentration
as shown below. The effect has been determined after
or phosphinic acid-(p-alkylmercaptophenyl-mercapto
24 hours by counting the dead pests either on the surface
ethyl)-esters (or amides).
of the soil or still remaining on the plants. The follow
The p-alkylmercapto-thiophenols which have hitherto
ing results have been obtained:
not been described in the literature, may be used as start
ing materials for the production of insecticidal phosphoric 20
acid esters.
The aforesaid p-alkylmercapto-thiophenols
aqueous con
may be obtained, in an analogous manner to that for sim
centration (in
Compound
ilar compounds, from the readily obtainable p-alkylmer
captophenyl-sulfonic acid chlorides by reduction with zinc
By condensation of p-alkylmercapto~thiophenols with
ethylene bromide or chlorobromethane there vmay readily
be obtained the ?-bromethyl- or B-chlorethyl-(-p-alkyl
mercaptophenyl)-thioethers of the following formula
30
(in percent)
ingredient]
water)
25
dust.
killing rate
percent active
(I) ____________________________________ __
0.0001
100
(II) ___________________________________ -_
0.01,
100
(11) against spider mites (contact-insecticidal action).
Bean plants (Phaseolus vulgaris) of about 15 inches
height are sprayed drip Wet with solutions as prepared
above in a concentration as shown below. The bean
The reaction of ?-bromo-(or -ch1oro-)-ethyl-(p-alkyl
mercaptophenyl)-thioethers with salts of monothio~or
35
dithiophosphoric, -phosphonic or -phosphinic acid esters
or amides there are obtained in good yields compounds
plants have been infested heavily with the two-spotted
spider (species T etranychus telarius). Evaluation has
been carried out after 24 hours, 48 hours and 8 days.
The following results have been obtained:
of the following general formula
aqueous con
40
In the above formula R1 and R2 stand for alkoxy 45
groups, preferably containing 1-4 carbon atoms, for ali
phatic or aromatic radicals or amino groups which may
be substituted.
centration (in
Compound
percent active
ingredient]
water)
(I) ____________________________________ __
(II) ___________________________________ __
killing rate
(in percent)
0. 01
0. 0001
100
90
The following examples are given for the purpose of
illustrating the process according to the invention.
The new compounds are distinguished in addition to a
Example 1
good contact activity against insects by a markedly ovicidal 50
action especially against the eggs of the red spider. The
s
00H,
new esters may also be used with good results against
eating pests such as caterpillars. They may be used in
the same manner as other known phosphoric insecticides,
i.e. in a concentration from about 0.00001% to about 55
'
OCH;
40 grams (0.2 mol) of dimethyl-dithiophosphoric acid
1%, diluted or extended with suitable solid or liquid
carriers or diluents. Examples of such solid carriers are
ammonium salt are dissolved in 75 cc. of methyl ethyl
ketone; 30 cc. of dimethyl formamide and 53 grams (0.2
talc, chalk, bentonite, clay and the like, as liquid car
mol) of ?-bromethyl-(p-methylmercaptophenyl) - thio
ether (M. P. 51° C.) are then added at 40° C. The mix
riers there may be mentioned, water (if necessary with
ture is heated to 70° C. with stirring for one hour, and
the reaction product then allowed to cool. The reaction
product is poured into 500 cc. of ice water. The precipi
tated oil is taken up in benzene. The benzene solution is
liquid hydrocarbons and the like. The new compounds
thoroughly washed with water and subsequently dried
may furthermore be used in combination with each other
65 with sodium sulfate. The benzene is distilled oii in a
or with known insecticides, fertilizers etc.
vacuum. 34 grams of a pale yellow water-insoluble oil
As examples for the special utility of the inventive
remain which may be distilled only with decomposition
compounds the compounds of the following formulae
commercial emulsi?ers), alcohols, especially lower al
cohols such as methanol 01' ethanol, ketones, especially
lower ketones such as acetone or methyl ethyl ketone,
(1)
S
001B:
even in a high vacuum. Yield 50% of the theoretical.
On rats per es the new compound shows a toxicity of
100 mg./ kg. LD50. Mosquito larvae are killed completely
with 0.001% solutions and aphids are killed to 60% with
002K:
0.001%
solutions.
.
.
'
3,021,351
A.
By the same way there may be obtained the following
3
By exactly the same way there may be obtained the fol
lowing compounds:
‘
compounds:
'
"
s
003E171
0 0.1111
10
0 (331171
Example 5
15
CH;
20 grams (0.1 mol) of methyl-O-methyl ester-dithio
phosphonic acid potassium salt are dissolved in 75 cc. of
acetonitrile. 27 grams (0.1 mol) of 'B-bromoethyl-(p
45 grams ( 0.2 mol) of diethyl-dithiophosphoric acid
20 methyl-mercaptophenyl)-thioether in 75 cc. of acetonitrile
are added with; stirring at 60~70° C. The mixture is
kept at 70° C. vfor 2 hours and then worked up in usual
‘ammonium salt are dissolved in 70 cc. of methyl ethyl
ketone. 53 grams (0.2 mol) of B-bromoethyl-(p-methyl
manner. 28 grams of the new ester are thus obtained in
mercapto-phenyl)-thioether, dissolvedrin 30 cc. of di—_
the form of a pale yellow water-insoluble oil.v Yield 86%
methyl formamide, are added with stirring. The mixture 25
of the theoretical.
>
.
is heated to 70° C. for one hour and then worked up as
described in Example 1. 40 grams of the new ester are
thus obtained as a yellow water-insoluble oil. Yield 55%
Calculated for mol 325 ; S, 39.4%; P, 9.5%. Found:
S, 39.0%; P, 9.0%. On rats per os toxicity 2.5 mg./kg.
LD5O. Spider mites were killed completely with 0.001%
of the theoretical. .
solutions, aphids with 0.01% solution, mosquito larvae
a
The physical data are as follows: d42° 1.235; 121320 30 with 0.00001% solutions and caterpillars with 0.1% solu
1.6115. On rats per os toxicity'5 mgJkg. LD5O. Sys
tions, Systemic action'with 0.1% solutions=100%.
temic action on spider mites with 0.1% solutions=100%.
By exactly the same way there may be obtained the
The compound has an ovicidal action.
following compound:
1
"
r’
'
Example 3
O OCzHs
35
;
s
onas~®-s-onr-onz_s—iy
_
50 grams (0.2 mol) of diethyl-monothiophosphoric
\orm
Example 6
0 CrHl
acid ammonium salt are dissolved in 70 cc. of methyl
'
00H,
40
S 002E;
ethyl ketone. A solution of. 53 grams (0.2 mol) of 18-.
bromoethyl-(p-methyl-mercapto-phenyl)-thioether in 40
cc. of dimethyl formamide are then added with stirring.
The temperature is kept at 70° C. for 2 hours and the
product then worked up in usual manner. 68 grams of
22 grams (0.1 mol) of methyl—O-ethyl ester-dithio
phosphonic acid potassium salt are dissolved in 50 cc. of
acetonitrile.
the new ester'are thus obtained as a yellow watereinsoluble'
oil.
Yield 95% of the theoretical.~
-
a
The physical constants area's followsi d4” 1.205; 'riDzo
1.5719. On rats 'per os LD50 5 rug/kg. Aphid’s'are'
killed completely with 0.001% solutions and spider mites
in usual manner. 31 grams of the'new ester are thus
obtained as a yellow water-insoluble oil. Yield 91% of
are killed completely with 0.01% solutions.
By exactly the same way there may be obtained the
following compound:
‘
'
27 grams (0.1 mol) of B-bromoethyl-(p
methyl-mercaptophenyl)-thioether, dissolved in 75 cc. of
acetonitrile, are then added at 70° C. with stirring. The
mixture is kept at 75° C. for 2 hours and then worked up
a
the theoretical.
'
‘
Calculated for mol 338: S, 37.9%; P, 9.1%. Found:
S, 37.9%; P, 9.0%. On rats per os LD5Q 2.5 mgJkg.
Caterpillars are k1ll€d completely with 0.1% solutions.
Example 7
"
S
OC2H5
60
23 grams (0.1 mol) of ethyl-O-ethyl ester-dithio
phosphonic acid potassium salt are dissolved in 50 cc. of
55 grams (0.2 mol) of diisopropyl-dithiophosphoric
acetonitrile. ' 27 grams (0.1 mol) of ?-bromoethyl-(p
acid ammonium salt are dissolved in 70 cc. of methyl 65 methylmercaptophenyl)-thioether, dissolved in 75 cc. of
ethyl ketone. A solution of 53 grams of ?-bromoethyl
acetonitrile, are then added at 70° C. with stirring. The
(p-methylmercapto-phenyl)-thioether in 30 cc. of dimeth—
mixture is kept at 75—80° C. for 2 hours and then worked
yl'formamide is then added with stirring. The mixture
is, kept at 80°C. for 2 hours and then worked up in
usual manner.
77 grams of the new ester are thus ob
tained as a pale yellow water-insoluble oil. Yield 93%
up in usual manner.
32 grams of the new ester are ob
tained as a yellow water-insoluble oil.‘ Yield 90% of
70
the theoretical.
,
Calculated for mol 353: S, 36.25%; P, 8.7%. Found:
of the theoretical.
.
r
'
S, 37.0%; P, 8.9%. On rats per os toxicity 2.5 mg./kg.
.The physical data are the following: d4” 1.170; nD2°
LDso. Aphids are killed completely with 0.001% solutions
15880; On rats per os LD50 100.mg./kg. Aphids’are
and spider mites are killed to 90% with 0.0001% solu
killed to 90% with 0.001% solutions.
' 75 tions.
3,021,351
6
5
By exactly the’ same way there may be obtained the
S
following compound:
We claim:
1. The compound of the following formula
C4119
Example 8
S
0
02115
OOH:
09211;
10
0 0H,
. The compound of the following formula
21 grams (0.1 mol) of ethyl-phosphono-O-ethyl ester
S
thiolic acid potassium salt are dissolved in 50 cc. of aceto
OG2H5
nitrile. 27 grams (0.1 mol) of B-bromoethyl-(p-methyl
mercapto-phenyl)-thioether, dissolved in 75 cc. of aceto 15
nitrile, are then added at 60—70° C. with stirring. After
working up in the usual manner, 33 grams of the new
O C2H5
3. The compound of the following formula
0 OC2H5
ester are obtained as a colorless, scarcely water-soluble
oil.
Calculated for mol 336: S, 28.6%; P, 9.2%. Found: 20
S, 28.4%; P, 9.4%. On rats per os toxicity 1 mg./kg.
LDSO. Aphids are ldlled to 90% with 0.001% solutions
and spider mites are killed completely with 0.001% solu
tions. Systemic action with 0.1% solutions=l00%.
By exactly the same way there may be obtained the 25
following compounds:
OC2H5
4. A compound of the following formula '
S
OCH;
5. The compound of the following formula
0
CHgS-QS-CIIr-C m-s-rH /
O CzH;
H
O
S
30
6. The compound of the following formula
0 C211;
OH=C (CH3):
OCZHg
S
OCrHs
35
Example 9
7. The compound of the following formula
IS CH:
s
0H,
40
40 grams (0.2 mol) of dimethyl-thionothiolphosphinic
acid potassium salt are dissolved in 100 cc. of acetonitrile.
54 grams (0.2 mol) of B-bromoethyl-(p-methylmercapto
CH:
8. A phosphorous-containing compound of the follow
ing formula
phenyl)-thioether, dissolved in 100 cc. of acetonitrile, are
added at 65° C. with stirring. The mixture is kept at 65°
C. for 2 hours and then worked up in the usual manner.
57 grams of the new ester are obtained as a yellow water
in which R stands for a lower alkyl radical having up to
insoluble oil. Yield 92% of the theoretical.
four carbon atoms, R1 stands for a member selected
Calculated for mol 308: S, 41.5%; P, 10.0%. Found:
from the group consisting of a lower alkoxy radical hav
S, 41.3%; P, 9.5%. On rats per os toxicity 250 mg./kg. 50 ing up to four carbon atoms, a lower alkyl radical hav
LD5U. Spider mites are killed completely with 0.01% so
ing up to six carbon atoms, a lower alkenyl radical hav
lutions. Systemic action with 0.1% solutions=100%.
Example 10
S
C2135
ing up to 6 carbon atoms, an amino group, a lower
alkyl amino group having up to four carbon atoms and
a lower dialkyl amino group having up to four carbon
55 atoms, R: stands for a member selected from the group
consisting of a lower alkoxy group having up to four
carbon atoms, a .lower alkyl radical having up to six
carbon atoms lower alkenyl radical having up to 6 carbon
23 grams (0.1 mol) of diethyl-thionothiolphosphinic
acid potassium salt are dissolved in 50 cc. of acetonitrile. 60 atoms, cyclohexyl and a phenyl group, and X stands for
a chalcogen having an atomic weight between 16 and 33.
27 grams (0.1 mol) of ?-bromoethyL(p-methylmercapto
9. A phosphorus containing compound of claim 8
phenyl)-thioether, dissolved in 75 cc. of acetonitrile, are
wherein R1 and R2 each stand for a lower alkoxy radical
added at 70° C. with stirring. The mixture is kept at
having up to four carbon atoms.
75° C. for one hour and then worked up in the usual
03115
manner.
32 grams of the new ester are obtained as a
10. A phosphorus containing compound of claim 8
wherein R1 and R2 each stand for a lower alkyl radical
yellow water-insoluble oil. Yield 95% of the theoretical.
having up to six carbon atoms.
Calculated for mol 337: S, 38.0%; P, 9.2%. Found:
11. A phosphorus containing compound of claim 8
S, 38.1%; P, 9.2%. On rats per os toxicity 50 mgjkg.
wherein R1 stands for a lower alkoxy radical having up
LD5U. Spider mites are killed to 80% with 0.001% solu
to four carbon atoms and R2 stands for a lower alkyl
tions. Systemic action with 0.1% solutions=100%.
70 radical having up to six carbon atoms.
By exactly the same way there may be obtained the
following compound:
- No references cited.
UNITED S’I‘A'l ES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No, 3,021,351
February 13, 1962
Ernst Schegk et a1,
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 1I line 34, for "The" read ---~ By w; column 2,
line 58, for "[5-bromethyl—~“ read -=-— B—brom0ethy1— ——;
column 6, lines 33 to 35, the formula should appear as
shown below instead of as in the patent:
Signed and sealed this 21st day of August‘ 1962,
(SEAL)
Attest:
ESTON G. JOHNSON
Attesting Officer
DAVID L“ LADD
Commissioner of Patents
Документ
Категория
Без категории
Просмотров
0
Размер файла
420 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа