DE1040542B - Process for the preparation of thionophosphoric acid esters - Google Patents
Process for the preparation of thionophosphoric acid estersInfo
- Publication number
- DE1040542B DE1040542B DEF21904A DEF0021904A DE1040542B DE 1040542 B DE1040542 B DE 1040542B DE F21904 A DEF21904 A DE F21904A DE F0021904 A DEF0021904 A DE F0021904A DE 1040542 B DE1040542 B DE 1040542B
- Authority
- DE
- Germany
- Prior art keywords
- killed
- concentration
- preparation
- acid esters
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims description 9
- 150000002148 esters Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 3
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- 150000002019 disulfides Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 241001454295 Tetranychidae Species 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 241000255925 Diptera Species 0.000 claims 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 230000008030 elimination Effects 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 1
- 229910052753 mercury Inorganic materials 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1658—Esters of thiopolyphosphoric acids or anhydrides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Thionophosphorsäuieester, in denen die Reste zweier Dialkylthionophosphorsäuren über die Sulfoxydgruppe miteinander verknüpft sind, sind bisher nicht bekanntgeworden. Thionophosphoric acid esters, in which the residues of two Dialkylthionophosphoric acids are linked to one another via the sulfoxide group, have not yet become known.
Es wurde nun gefunden, daß diese Stoffklasse aus 0,0-Dialkyldithiophosphorsäure-disulnden folgender allgemeinen Formel:It has now been found that this class of substances consists of 0,0-dialkyldithiophosphoric acid disulndants of the following general Formula:
RO,RO,
RORO
P —S —S —P'P —S —S —P '
OROR
OROR
Verfahren zur Herstellung von ThionophosphorsäureesternProcess for the preparation of thionophosphoric acid esters
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-BayerwerkPaint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk
Dr. Gerhard Schrader, Wuppertal-Cronenberg, ist als Erfinder genannt wordenDr. Gerhard Schrader, Wuppertal-Cronenberg, has been named as the inventor
(vgl. USA.-Patentschrift 2 705 694; R = vorzugsweise (See U.S. Patent 2,705,694; R = preferably
niedrigmolekularen Alkylrest) leicht zugänglich ist, wenn »
die Oxydation so durchgeführt wird, daß ein Schwefelatom eliminiert wird und der verbleibende Brücken- oder Verdünnungsmitteln gemischt, zur Anwendung
schwefel zum Sulfoxyd oxydiert wird, wie aus folgendem ao gelangt.
Formelschema ersichtlich ist: SSlow molecular weight alkyl radical) is easily accessible if the oxidation is carried out in such a way that a sulfur atom is eliminated and the remaining bridging or diluent is mixed, sulfur is oxidized to the sulfoxide for use, as can be seen from the following ao.
Formula scheme can be seen: SS
C9ELO.C 9 ELO.
,p—so — p;, p — so - p;
tiS.
ti
[| S.
[|
C9ILOC 9 ILO
H2O2 C,H,0H 2 O 2 C, H, O
S SS S
;p s s ρ; p s s ρ
,OC2H5 , OC 2 H 5
OC2H5 OC 2 H 5
-OC2H5 -OC 2 H 5
RORO
RORO
OR äH50OR ä H 5 0
p—so—p:p — so — p:
+ S + H2O Insektizide Wirksamkeit + S + H 2 O insecticidal effectiveness
1OR 1 OR
Vorteilhaft wird dabei die Oxydation der Disulfide mit Wasserstoffsuperoxyd in geeigneten Lösemitteln in schwach saurem Medium bei Temperaturen von 40 bis 70° C durchgeführt. Bewährt hat sich als Lösemittel vor allem Eisessig. Es können aber auch Kohlenwasserstoffe als Lösemittel verwendet werden, wenn z. B. in Gegenwart geringer Mengen Schwefelsäure diese Reaktion durchgeführt wird.The oxidation of the disulfides with hydrogen peroxide in suitable solvents in carried out in a weakly acidic medium at temperatures of 40 to 70 ° C. Has proven itself as a solvent especially glacial acetic acid. However, hydrocarbons can also be used as solvents if, for. Am In the presence of small amounts of sulfuric acid this reaction is carried out.
Während die als Ausgangsmaterialien benötigten Disulfide praktisch keine kontaktinsektiziden Wirkungen zeigen, zeichnen sich die neuen Sulfoxyde durch gute kontaktinsektizide und zum Teil auch systemische Wirkungen aus (vgl. nachstehende Tabelle). Fliegen und Raupen z. B. können mit der erfindungsgemäßen Verbindung wirkungsvoll bekämpft werden, wobei die neue Stoffklasse vorzugsweise in der für Phosphorinsektizide bekannten Art und Weise, d. h. mit üblichen Streck-While the disulfides required as starting materials have practically no contact insecticidal effects show, the new sulfoxides are characterized by good contact insecticides and in some cases also systemic Effects (see table below). Flies and caterpillars z. B. can with the compound of the invention can be effectively combated, the new substance class preferably in the one for phosphorus insecticides known way, d. H. with the usual stretching
Fliegen 0,001 %Flying 0.001%
Blattläuse 0,001 %Aphids 0.001%
Spinnmilben 0,001 %Spider mites 0.001%
Küchenschaben 0,001 %Cockroaches 0.001%
100% 80% 50% 40%100% 80% 50% 40%
0,01% 0,01% 0,01% 0,1 %0.01% 0.01% 0.01% 0.1%
0%0%
0%0%
50%50%
0%0%
C9H=OC 9 H = O
C2H5OC 2 H 5 O
P —SO —P,P —SO —P,
OC2H5 OC 2 H 5
OC9H5 OC 9 H 5
74 g 0,0,0,0-Tetraäthylthionophosphorsäuredisulfid löst man in 100 ecm Eisessig unter Zugabe von 1 ecm 50%iger Schwefelsäure. Bei 40° C tropft man dann unter Rühren 27 ecm Wasserstoffsupeioxyd (37,5%ig) zu. Die Reaktion verläuft untei Selbsterwärmung. Nachdem die Reaktionswärme abgeklungen ist, hält man die Temperatur noch 1 Stunde bei 40° C, nimmt dann das Rohprodukt in 200 ecm Benzol auf und wäscht die Benzolschicht mit einer 3%igen Bikarbonatlösung. Nach74 g of 0,0,0,0-tetraethylthionophosphoric acid disulfide are dissolved in 100 ecm of glacial acetic acid with the addition of 1 ecm 50% sulfuric acid. At 40 ° C, 27 ecm of hydrogen peroxide (37.5%) are then added dropwise with stirring. to. The reaction is self-heating. After the heat of reaction has subsided, the temperature is kept at 40 ° C for 1 hour, then this is taken Crude product in 200 ecm benzene and washes the benzene layer with a 3% bicarbonate solution. To
809 657/465809 657/465
Claims (1)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE562442D BE562442A (en) | 1956-12-11 | ||
| NL97805D NL97805C (en) | 1956-12-11 | ||
| DEF21904A DE1040542B (en) | 1956-12-11 | 1956-12-11 | Process for the preparation of thionophosphoric acid esters |
| DEF23319A DE1046034B (en) | 1956-12-11 | 1957-06-24 | Process for the preparation of thionophosphoric acid esters |
| CH5277457A CH368157A (en) | 1956-12-11 | 1957-11-18 | Process for the preparation of thionophosphoric acid esters |
| CH294563A CH374650A (en) | 1956-12-11 | 1957-11-18 | Process for the preparation of thionophosphoric acid esters |
| FR1190076D FR1190076A (en) | 1956-12-11 | 1957-11-19 | Thionophosphoric esters and their production process |
| GB3840657A GB822476A (en) | 1956-12-11 | 1957-12-10 | Thionophosphoric acid esters and a process for their production |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF21904A DE1040542B (en) | 1956-12-11 | 1956-12-11 | Process for the preparation of thionophosphoric acid esters |
| DEF23319A DE1046034B (en) | 1956-12-11 | 1957-06-24 | Process for the preparation of thionophosphoric acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1040542B true DE1040542B (en) | 1958-10-09 |
Family
ID=25974004
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF21904A Pending DE1040542B (en) | 1956-12-11 | 1956-12-11 | Process for the preparation of thionophosphoric acid esters |
| DEF23319A Pending DE1046034B (en) | 1956-12-11 | 1957-06-24 | Process for the preparation of thionophosphoric acid esters |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF23319A Pending DE1046034B (en) | 1956-12-11 | 1957-06-24 | Process for the preparation of thionophosphoric acid esters |
Country Status (6)
| Country | Link |
|---|---|
| BE (1) | BE562442A (en) |
| CH (2) | CH374650A (en) |
| DE (2) | DE1040542B (en) |
| FR (1) | FR1190076A (en) |
| GB (1) | GB822476A (en) |
| NL (1) | NL97805C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1188859B (en) * | 1960-12-10 | 1965-03-11 | Basf Ag | Preparations for the control of insects |
| NL135594C (en) * | 1961-06-06 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE820001C (en) * | 1949-09-07 | 1951-11-08 | Bayer Ag | Process for the preparation of thiopyrophosphoric acid esters |
| US2705694A (en) * | 1952-06-24 | 1955-04-05 | Exxon Research Engineering Co | Insecticidal compositions comprising diethyl thiophosphoric acid disulfide |
-
0
- NL NL97805D patent/NL97805C/xx active
- BE BE562442D patent/BE562442A/xx unknown
-
1956
- 1956-12-11 DE DEF21904A patent/DE1040542B/en active Pending
-
1957
- 1957-06-24 DE DEF23319A patent/DE1046034B/en active Pending
- 1957-11-18 CH CH294563A patent/CH374650A/en unknown
- 1957-11-18 CH CH5277457A patent/CH368157A/en unknown
- 1957-11-19 FR FR1190076D patent/FR1190076A/en not_active Expired
- 1957-12-10 GB GB3840657A patent/GB822476A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR1190076A (en) | 1959-10-09 |
| DE1046034B (en) | 1958-12-11 |
| NL97805C (en) | |
| CH374650A (en) | 1964-01-31 |
| CH368157A (en) | 1963-03-31 |
| GB822476A (en) | 1959-10-28 |
| BE562442A (en) |
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