DE1177153B - Process for the preparation of alkyldithio-phosphonic acid-S- [1,2-bis- (alkoxycarbonyl) -aethyl] -O-alkyl esters - Google Patents
Process for the preparation of alkyldithio-phosphonic acid-S- [1,2-bis- (alkoxycarbonyl) -aethyl] -O-alkyl estersInfo
- Publication number
- DE1177153B DE1177153B DEST19597A DEST019597A DE1177153B DE 1177153 B DE1177153 B DE 1177153B DE ST19597 A DEST19597 A DE ST19597A DE ST019597 A DEST019597 A DE ST019597A DE 1177153 B DE1177153 B DE 1177153B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- coor
- general formula
- cooc
- ester
- 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
- 238000000034 method Methods 0.000 title claims description 13
- 125000004453 alkoxycarbonyl group Chemical group 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- -1 dithiophosphonic acid ester halide Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- FLQUDUCNBDGCRI-UHFFFAOYSA-N hydroxy-sulfanyl-sulfidophosphanium Chemical compound SP(S)=O FLQUDUCNBDGCRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- HGELWZQRZUOEOJ-UHFFFAOYSA-N ethyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCP(O)(O)=S HGELWZQRZUOEOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012552 review Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 241000238631 Hexapoda Species 0.000 description 9
- GFTATZBXSYXGRK-UHFFFAOYSA-N ethyl-hydroxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCP(O)(S)=S GFTATZBXSYXGRK-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241000254173 Coleoptera Species 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000238876 Acari Species 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 241000238675 Periplaneta americana Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 244000207543 Euphorbia heterophylla Species 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000642 acaricide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- DXVBUJOATHQUCY-UHFFFAOYSA-N hydroxy-methyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CP(O)(S)=S DXVBUJOATHQUCY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- WXJXBKBJAKPJRN-UHFFFAOYSA-N Methanephosphonothioic acid Chemical compound CP(O)(O)=S WXJXBKBJAKPJRN-UHFFFAOYSA-N 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000258913 Oncopeltus fasciatus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 241000254112 Tribolium confusum Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- ZKDXOQLMFFSKTG-UHFFFAOYSA-N ethoxy-ethyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(S)(=S)CC ZKDXOQLMFFSKTG-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- BFBJAIUYHVCZNN-UHFFFAOYSA-N hydroxy-methoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound COP(O)(S)=S BFBJAIUYHVCZNN-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ARENMZZMCSLORU-UHFFFAOYSA-N propan-2-yl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)OC(C)C)=CC=CC2=C1 ARENMZZMCSLORU-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
Description
BUNDESREPUBLIK DEUTSCHLAND Internat. KL: C07f FEDERAL REPUBLIC OF GERMANY Internat. KL: C07f
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Deutsche KL: 12 ο -26/01 German KL: 12 ο -26/01
Nummer: 1177153Number: 1177153
Aktenzeichen: St 19597IV b / 12 οFile number: St 19597IV b / 12 ο
Anmeldetag: 16. August 1962Filing date: August 16, 1962
Auslegetag: 3. September 1964Opening day: September 3, 1964
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Alkyldithiophosphonsäure-S-[1 ,l-bis-ialkoxycarbony^-äthylJ-O-alkylestern. Diese Verbindungen sind überlegene Wirkstoffe in der Schädlingsbekämpfung.The present invention relates to a process for the preparation of alkyldithiophosphonic acid-S- [1 , l-bis-alkoxycarbony ^ -äthylJ-O-alkyl esters. These Compounds are superior agents in pest control.
Die erfindungsgemäß herstellbaren Verbindungen haben die allgemeine FormelThe compounds which can be prepared according to the invention have the general formula
Verfahren zur Herstellung von Alkyldithio-Process for the production of alkyldithio-
phosphonsäure-S-[l,2-bis-(alkoxycarbonyl)-phosphonic acid-S- [1,2-bis- (alkoxycarbonyl) -
äthyl]-O-alkylesternethyl] -O-alkyl esters
R-P-S-CH-COOR2 RPS-CH-COOR 2
ORiORi
CH2 — COOR3 CH 2 - COOR 3
in der R, Ri, R2 und R3 Alkylreste mit 1 bis 4 C-Atomen darstellen.in which R, Ri, R2 and R3 are alkyl radicals with 1 to 4 carbon atoms represent.
R2 und R3 bedeuten vorzugsweise Methyl oder Äthyl.R2 and R3 are preferably methyl or ethyl.
Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß man in jeweils an sich bekannter Weise entweder einen Dithiophosphonsäuremonoester der allgemeinen FormelThe process according to the invention is characterized in that one is in each case known per se Way either a dithiophosphonic acid monoester of the general formula
Anmelder:Applicant:
Stauffer Chemical Company, New York, N. Y.Stauffer Chemical Company, New York, N.Y.
(V. St. A.)(V. St. A.)
Vertreter:Representative:
Dipl.-Chem. Dr. jur. W. Beil, A. Hoeppener
und Dr. H. J. Wolff, Rechtsanwälte,
Frankfurt/M.-Höchst, Antoniterstr. 36Dipl.-Chem. Dr. jur. W. Beil, A. Hoeppener
and Dr. HJ Wolff, lawyers,
Frankfurt / M.-Höchst, Antoniterstr. 36
Als Erfinder benannt:Named as inventor:
Karoly Szabo, New York, N. Y. (V. St. A.)Karoly Szabo, New York, N.Y. (V. St. A.)
R —P —SH
OR1 R-P-SH
OR 1
in der R und Ri die vorstehend angegebene Bedeutung haben, mit einem niederen Alkylester einer aliphatischen Dicarbonsäure der allgemeinen Formelin which R and Ri have the meaning given above, with a lower alkyl ester of an aliphatic one Dicarboxylic acid of the general formula
CH-COOR2
CH — COOR3 CH-COOR 2
CH - COOR 3
in der R2 und R3 die vorstehend angegebene Bedeutung haben, oder ein Dithiophosphonsäureesterhalogenid der allgemeinen Formelin which R2 and R3 have the meaning given above have, or a dithiophosphonic acid ester halide of the general formula
R — P — Halogen
ORiR - P - halogen
ORi
in der R und Ri die vorstehend angegebene Be-Beanspruchte Priorität:in the R and Ri the above-mentioned Be-stressed Priority:
V. St. v. Amerika vom 18. August 1961 (132 315)V. St. v. America August 18, 1961 (132 315)
deutung haben, mit einem Mercaptobernsteinsäureester der allgemeinen Formelhave meaning, with a mercaptosuccinic acid ester of the general formula
HS —CH-COOR2HS — CH-COOR2
CH2 — COOR3CH 2 - COOR3
in der R2 und R3 die vorstehend angegebene Bedeutung haben, umsetzt.in which R 2 and R3 have the meaning given above.
Andere Derivate der Thiosäuren des Phosphors sind bekannt. Das in seiner Struktur den erfindungsgemäß hergestellten Verbindungen am nächsten kommende Derivat ist der Methoxydithiophosphonsäure-S-fl^-bis-iäthoxycarbony^-äthylJ-O-methylester. Die erfindungsgemäß herstellbaren Verbindungen sind diesem Ester und anderen bekannten strukturferneren Verbindungen überlegen, wie folgende Übersicht beweist:Other derivatives of the thioacids of phosphorus are known. That in its structure according to the invention The closest derivative produced is the methoxydithiophosphonic acid S-fl ^ -bis-iäthoxycarbony ^ -äthylJ-O-methyl ester. The compounds which can be prepared according to the invention are this ester and others known consider more structurally distant connections, as the following overview shows:
409 659/455409 659/455
RahmenFalling into the
frame
tr O V^ Π2 *^ΛΛ_^>Γ15
/
C2H5OV - 2 * "i5 O
tr OV ^ Π2 * ^ ΛΛ _ ^> Γ15
/
C 2 H 5 O
P-S-CH2-COOC2H5
C2H5OC 2 H 5 OS
PS-CH 2 -COOC 2 H 5
C 2 H 5 O
CH3O-P-S-CH-COOC2H5 Il
CH 3 OPS-CH-COOC 2 H 5
I! S.
I!
Μ S.
Μ
KF = Küchenfliege,
AKS = amerikanische Küchenschabe,KF = kitchen fly,
AKS = American cockroach,
WMK = Wolfsmilchkäfer, FMK = falscher Mehlkäfer,WMK = milkweed beetle, FMK = false flour beetle,
2PM = 2-Punkt-MiIbe,
2PMe = Eier der 2-Punkt-Milbe.2PM = 2-point mite,
2PMe = eggs of the 2-point mite.
Die Versuche wurden entsprechend dem folgenden Bewertungstest durchgeführt. Die angegebenen Werte sind sämtlich LDäo-Werte, im Falle der Küchenfliege und des falschen Mehlkäfers angegeben in Mikro gramm zur Erzielung dieses Ergebnisses erforderlicher Substanz, im Falle der anderen Insekten in Prozenten aktiver Substanz in der angewandten Lösung.The experiments were carried out according to the following evaluation test. The stated values are all LDäo values, in the case of the kitchen fly and the meal beetle, expressed in micrograms, is more necessary to achieve this result Substance, in the case of the other insects as a percentage of the active substance in the applied Solution.
Bewertungstest über milbentötende WirkungEvaluation test on miticide effect
Die 2-Punkt-Milbe, Tetranychus telarius (Linn.), wird in den Testverfahren für milbentötende Mittel verwendet. Junge »Pinto«-Bohnenpflanzen werden mit mehreren hundert Milben infiziert. Dispersionen der zu untersuchenden Verbindungen werden hergestellt, indem man 0,1 g des toxischen Stoffes in 10 ecm Aceton löst. Darauf wird diese Lösung mit Wasser verdünnt, in dem 0,015% des Natriumsalzes des Isopropylnaphthalinsulfonats und 0,005% methylierte Zellulose als Emulgiermittel enthalten sind; die Wassermenge wird so bemessen, daß die Konzentrationen des aktiven Bestandteiles zwischen 0,25 und 0,005% liegen. Diese Testsuspensionen werden dann auf die infizierten Pinto-Bohnenpflanzen gespritzt. Nach 7 und nach 14 Tagen werden die Pflanzen sowohl auf nachembryonale Formen der Milben als auch auf Eier untersucht. Der Prozentsatz der vernichteten Tiere wird durch Vergleich mit Kontrollpflanzen, die nicht gespritzt worden waren, ermittelt, der LDso-Wert wird unter Anwendung bekannter Verfahren errechnet. Die LDso-WerteThe 2-point mite, Tetranychus telarius (Linn.), Is used in the testing procedure for miticides used. Young "pinto" bean plants are infected with several hundred mites. Dispersions of the compounds under investigation are prepared by adding 0.1 g of the toxic substance in 10 ecm of acetone dissolves. This solution is then diluted with water containing 0.015% of the sodium salt the isopropyl naphthalene sulfonate and 0.005% methylated cellulose are included as emulsifying agents; the amount of water is calculated so that the concentrations of the active ingredient between 0.25 and 0.005%. These test suspensions are then applied to the infected pinto bean plants injected. After 7 and after 14 days, the plants are both on postembryonic forms of the Both mites and eggs were examined. The percentage of animals destroyed is determined by comparison with Control plants that had not been sprayed, the LD 50 value is determined using calculated using known methods. The LDso values
werden in der Tabelle unter den Spalten »2 PM« und »2 PMe« angegeben.are specified in the table under the columns "2 PM" and "2 PMe".
Bewertungstest über insektentötende WirkungEvaluation test for insecticidal effect
Vier Arten von Insekten wurden dem Bewertungstest für Insektizide unterworfen: Four kinds of insects were subjected to the insecticide evaluation test:
1. Amerikanische Küchenschabe (AKS),
Periplaneta americana (Linn.),1. American cockroach (AKS),
Periplaneta americana (Linn.),
2. Wolfsmilchkäfer (WMK),
Oncopeltus fasciatus (Dallas),2. milkweed beetle (WMK),
Oncopeltus fasciatus (Dallas),
3. Falscher Mehlkäfer (FMK),
Tribolium confusum (Duval),3. False meal beetle (FMK),
Tribolium confusum (Duval),
4. Küchenfliege (KF),4. Kitchen fly (KF),
Musca domestica (Linn.).Musca domestica (Linn.).
Das bei Insekten angewendete Verfahren stimmt mit dem Testverfahren für Milben überein. Die Versuchsinsekten werden in zum Postversand verwendete Papprohre (Durchmesser 7,9 cm, Länge 6,7 cm) eingesperrt. Die Käfige erhalten Zellophanböden und durchlöcherte Deckel. In jeden Käfig werden zehn bis fünfundzwanzig Insekten gesetzt.The procedure used for insects is the same as the test procedure for mites. the Test insects are placed in cardboard tubes (diameter 7.9 cm, length 6.7 cm) imprisoned. The cages have cellophane bottoms and perforated lids. In every cage ten to twenty-five insects are placed.
Go Jeder Käfig erhält Nahrung und Wasser. Die falschen Mehlkäfer werden ohne Nahrung in Petrischalen gebracht. Die eingesperrten Insekten werden mit der aktiven Verbindung in verschiedenen Konzentrationen besprüht. Nach 24 und 72 Stunden werden die lebenden und toten Insekten ausgezählt.Go Each cage receives food and water. The wrong ones Flour beetles are placed in petri dishes without food. The caged insects are with the active compound sprayed in different concentrations. After 24 and 72 hours will be the living and dead insects are counted.
Die Bewertungsuntersuchungen für Hausfliegen sind etwas anders; das giftige Mittel wird in einem flüchtigen Lösungsmittel, vorzugsweise Aceton, ge-The evaluation studies for house flies are slightly different; the poisonous agent is in one volatile solvent, preferably acetone,
löst, die aktive Verbindung wird auf den Boden einer Petrischale pipettiert, man läßt sie an der Luft trocknen und stellt sie dann in ein solches Papprohr. Fünfundzwanzig weibliche Fliegen werden in das Rohr eingesperrt. Die Fliegen werden dem bekannten Rückstand der aktiven Verbindung in dem Käfig ständig ausgesetzt. Nach 24 und 48 Stunden werden die lebenden und toten Insekten ausgezählt. Die LD50-Werte werden nach bekannten Verfahren ermittelt, sie sind in der nachstehenden Tabelle aufgeführt.dissolves, the active compound is pipetted onto the bottom of a Petri dish, it is left in the air dry and then put them in such a cardboard tube. Twenty-five female flies are in that Locked pipe. The flies will keep the known residue of the active compound in the cage exposed. After 24 and 48 hours, the live and dead insects are counted. The LD50 values are determined by known methods, they are listed in the table below.
Wirksamkeit gegen Insekten und MilbenEffectiveness against insects and mites
In den Rahmen der Erfindung fallen folgende Verbindungen:The following compounds fall within the scope of the invention:
Methyldithiophosphonsäure-S-[l,2-bis-(äthoxycarbonyl)-äthyl]-O-methylester Äthyldithiophosphonsäure-S- [ 1,2-bis-(äthoxycarbonyl)-äthyl]-O-isopropylester Methyldithiophosphonic acid S- [1,2-bis (ethoxycarbonyl) ethyl] -O-methyl ester Ethyldithiophosphonic acid S- [1,2-bis (ethoxycarbonyl) ethyl] -O-isopropyl ester
H3C-P-SH 3 CPS
OCH3
Strohfarbiges öl; nl5 = 1,5138.OCH 3
Straw-colored oil; nl 5 = 1.5138.
CH-COOC2H5 CH2-COOC2H5 CH-COOC 2 H 5 CH 2 -COOC 2 H 5
Methyldithiophosphonsäure-S-[l,2-bis-(äthoxycarbonyl)-äthyl]-O-äthylester Methyldithiophosphonic acid S- [1,2-bis (ethoxycarbonyl) ethyl] -O-ethyl ester
IlIl
H3C — P — S — CH — COOC2H5H 3 C - P - S - CH - COOC2H5
OC2H5 CH2-COOC2H5 Blaßgelbes öl; nf = 1,5076.OC 2 H 5 CH 2 -COOC 2 H 5 pale yellow oil; nf = 1.5076.
Äthyldithiophosphonsäure-S-[l,2-bis-(äthoxycarbonyI)-äthyl]-O-äthylester Ethyldithiophosphonic acid S- [1,2-bis (äthoxycarbonyI) ethyl] -O-ethyl ester
S
H5C2 — P — S — CH — COOC2H5 S.
H 5 C 2 - P - S - CH - COOC 2 H 5
OC2H5 CH2-COOC2H5 OC 2 H 5 CH 2 -COOC 2 H 5
Farbloses öl;«!5= 1,5029.Colorless oil; «! 5 = 1.5029.
Äthyldithiophosphonsäure-S-[l,2-bis-(methoxycarbonyl)-äthyl]-O-äthylester Ethyldithiophosphonic acid S- [1,2-bis (methoxycarbonyl) ethyl] -O-ethyl ester
S
H5C2 — P — S — CH — COOCH3 S.
H 5 C 2 - P - S - CH - COOCH 3
OC2H5 CH2-COOCH3 Gelbes öl;«?= 1,5129.OC 2 H 5 CH 2 -COOCH 3 yellow oil; «? = 1.5129.
H5C2- P-H 5 C 2 - P-
CH-COOC2H5CH-COOC2H5
0-CH(CHs)2 CH2-COOC2H5 Gelbes öl; US'= 1,4997.0-CH (CHs) 2 CH 2 -COOC 2 H 5 yellow oil; US '= 1.4997.
Äthyldithiophosphonsäure-S-[l,2-bis-(äthoxycarbonyl)-äthyl]-O-methylester Ethyldithiophosphonic acid S- [1,2-bis (ethoxycarbonyl) ethyl] -O-methyl ester
H5C2 — P — S — CH — COOC2H5 H 5 C 2 - P - S - CH - COOC 2 H 5
I II I
OCH3 CH2 — COOC2H5OCH 3 CH 2 - COOC2H5
Blaßgelbes öl; nls = 1,5090.Pale yellow oil; nl s = 1.5090.
Die Umsetzung wird durch Verwendung bestimmter Katalysatoren erleichtert, wie tert.Amine, z. B. Pyridin, Trialkylamine, z. B. Trimethylamin, Trräthylamin und durch Polymerisationsinhibitoren, wie Hydrochinon und dessen alkylierte Derivate, besonders die, die Alkylgruppen in den 2,4-Stellungen enthalten; für die Durchführung der Umsetzung erwiesen sich leicht erhöhte Temperaturen ebenfalls als günstig.The implementation is facilitated by using certain catalysts, such as tertiary amines, e.g. B. Pyridine, trialkylamines, e.g. B. trimethylamine, triethylamine and polymerization inhibitors, such as hydroquinone and its alkylated derivatives, especially those having the alkyl groups in the 2,4-positions contain; Slightly elevated temperatures were also found to carry out the reaction as cheap.
Wendet man die Additionsmethode eines Dithiophosphonsäuremonoesters an Äthylendicarbonsäureester an, so ist die Gegenwart einer Base vorteilhaft; als Beispiel wird hier ebenfalls auf die bereits erwähnten tertiären Amine verwiesen. Unabhängig von dem im einzelnen Fall angewandten Herstellungsverfahren erwies sich die Verwendung eines organisehen Lösungsmittels als vorteilhaft, sehr geeignet in diesem Zusammenhang sind die flüssigen aromatischen Kohlenwasserstoffe, z. B. Benzol, Toluol, Xylol, Methylnaphthalin.If the addition method of a dithiophosphonic acid monoester is used on ethylenedicarboxylic acid ester, the presence of a base is advantageous; as an example, reference is also made here to those already mentioned tertiary amines. Regardless of the manufacturing process used in the individual case The use of an organic solvent proved to be advantageous, very suitable in this context the liquid aromatic hydrocarbons, e.g. B. benzene, toluene, Xylene, methylnaphthalene.
Beispiel l(a)Example l (a)
Äthyldithiophosphonsäure-S-[l,2-bis-(äthoxycarbonyl)-äthyl]-O-äthylester Ethyldithiophosphonic acid S- [1,2-bis (ethoxycarbonyl) ethyl] -O-ethyl ester
M ethyldithiophosphonsäure-S-[ 1,2-bis-(äthoxycarbonyl)-äthyl]-O-methylester M ethyldithiophosphonic acid S- [1,2-bis (ethoxycarbonyl) ethyl] -O-methyl ester
H5C2 — P — S — CH — COOC2H5 H 5 C 2 - P - S - CH - COOC 2 H 5
OC2H5 CH2 — COOC2H5 OC 2 H 5 CH 2 - COOC 2 H 5
15,5 g Thioäpfelsäurediäthylester, 13,0 g Äthylthiophosphonsäurechlorid-O-äthylester, 60 ecm Aceton und 70 ecm Benzol wurden in einen Kolben gebracht, '5 der mit einem Rückflußkühler, einem Tropftrichter, einem Rührwerk und einem Thermometer versehen war. Unter gründlichem Rühren wurden 8,0 g Triäthylamin tropfenweise zugefügt; es trat eine sofortige Umsetzung ein mit gleichzeitiger Ausfällung des ^o Aminhydrochlorids. Nachdem die Zugabe beendet war, wurde das Reaktionsgemisch 30 Minuten unter Rückfluß erhitzt. Nachdem es auf Raumtemperatur abgekühlt worden war, wurde das Aminsalz abfiltriert, das Filtrat wurde, nachdem es mit 70 ecm Benzol gemischt worden war, mit Wasser, 3°/oiger wäßriger Natriumhydroxydlösung und wieder mit Wasser gewaschen. Das Filtrat wurde mit wasserfreiem Magnesiumsulfat getrocknet und darauf das Lösungsmittel im Vakuum entfernt. Es wurde ein fast farbloser öliger Rückstand gewonnen.15.5 g of thio malic acid diethyl ester, 13.0 g of ethylthiophosphonic acid chloride-O-ethyl ester, 60 ecm of acetone and 70 ecm of benzene were placed in a flask, '5 which is provided with a reflux condenser, a dropping funnel, a stirrer and a thermometer was. 8.0 g of triethylamine were added dropwise with thorough stirring; there was an immediate one Implementation with simultaneous precipitation of the ^ o amine hydrochloride. After the addition is over the reaction mixture was refluxed for 30 minutes. After it's at room temperature had been cooled, the amine salt was filtered off, the filtrate after it was at 70 ecm Benzene had been mixed with water, 3% aqueous sodium hydroxide solution and again with Water washed. The filtrate was dried with anhydrous magnesium sulfate and then the Solvent removed in vacuo. An almost colorless oily residue was obtained.
Ausbeute 20,5 g; nf = 1,5029. Die Verbindung des Beispiels 1 konnte wahlweise auch nach folgender Methode hergestellt werden:Yield 20.5 g; nf = 1.5029. The compound of Example 1 could optionally also be produced by the following method:
Beispiel l(b)Example l (b)
13,0 g Äthyldithiophosphonsäure-O-äthylester und 15,5 g Maleinsäurediäthylester wurden in Gegenwart von Hydrochinon in Benzol zum Rückfluß erhitzt. Nach Entfernung des Lösungsmittels verblieb ein Rückstand, der aus einem fast farblosen öl bestand. Die Analyse zeigte, daß die Struktur dieser Verbindung mit dem Ester identisch war, der nach dem Verfahren des Beispiels l(a) hergestellt worden H3C — P — S — CH — COOC2H5 13.0 g of ethyldithiophosphonic acid O-ethyl ester and 15.5 g of maleic acid diethyl ester were refluxed in the presence of hydroquinone in benzene. After removal of the solvent, a residue remained which consisted of an almost colorless oil. Analysis indicated that the structure of this compound was identical to the ester prepared by the procedure of Example 1 (a) H 3 C - P - S - CH - COOC 2 H 5
OCH3 CH2 — COOC2H5 OCH 3 CH 2 - COOC 2 H 5
Äthyldithiophosphonsäure-S-[l,2-bis-(äthoxycarbonyl)-äthyl]-O-methylester nf = 1,5138.Ethyldithiophosphonic acid S- [1,2-bis (ethoxycarbonyl) ethyl] -O-methyl ester nf = 1.5138.
Das Verfahren des Beispiels l(a) wurde unter Verwendung von Methylthiophosphonsäurechlorid-O-methylester wiederholt. Die Ergebnisse und Ausbeuten Hefen mit denen parallel, die im Beispiel l(a) erzielt worden waren.The procedure of Example 1 (a) was performed using methylthiophosphonic acid chloride-O-methyl ester repeated. The results and yields of yeasts in parallel with those in Example l (a) had been achieved.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13231561A | 1961-08-18 | 1961-08-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1177153B true DE1177153B (en) | 1964-09-03 |
Family
ID=22453449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEST19597A Pending DE1177153B (en) | 1961-08-18 | 1962-08-16 | Process for the preparation of alkyldithio-phosphonic acid-S- [1,2-bis- (alkoxycarbonyl) -aethyl] -O-alkyl esters |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE621471A (en) |
| CH (1) | CH413485A (en) |
| DE (1) | DE1177153B (en) |
| GB (1) | GB952698A (en) |
| NL (1) | NL282213A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE847897C (en) * | 1950-03-02 | 1952-08-28 | American Cyanamid Co | Process for the preparation of dithiophosphoric acid triesters |
| DE1058055B (en) * | 1957-09-28 | 1959-05-27 | Bayer Ag | Process for the preparation of phenylthionophosphonic acid esters |
| DE1067016B (en) * | 1954-12-04 | 1959-10-15 | Farbenfabriken Bayer Aktiengesellschaft Leverkusen-Bayerwerk | Process for the manufacture of organic phosphorus compounds |
| BE599323A (en) * | 1960-01-22 | 1961-02-12 | Bayer Ag | Process for the preparation of alkyl- or arylmercapto-carboxylic acid derivatives |
-
0
- NL NL282213D patent/NL282213A/xx unknown
- BE BE621471D patent/BE621471A/xx unknown
-
1962
- 1962-08-02 CH CH923862A patent/CH413485A/en unknown
- 1962-08-07 GB GB3020262A patent/GB952698A/en not_active Expired
- 1962-08-16 DE DEST19597A patent/DE1177153B/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE847897C (en) * | 1950-03-02 | 1952-08-28 | American Cyanamid Co | Process for the preparation of dithiophosphoric acid triesters |
| DE1067016B (en) * | 1954-12-04 | 1959-10-15 | Farbenfabriken Bayer Aktiengesellschaft Leverkusen-Bayerwerk | Process for the manufacture of organic phosphorus compounds |
| DE1058055B (en) * | 1957-09-28 | 1959-05-27 | Bayer Ag | Process for the preparation of phenylthionophosphonic acid esters |
| BE599323A (en) * | 1960-01-22 | 1961-02-12 | Bayer Ag | Process for the preparation of alkyl- or arylmercapto-carboxylic acid derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| CH413485A (en) | 1966-05-15 |
| GB952698A (en) | 1964-03-18 |
| NL282213A (en) | |
| BE621471A (en) |
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