DE1695181C - 0.0 Dialkyl S (2 halogen 1 N phthahmidoathyl) thiophosphate, Ver drive for their production and pesticides containing them - Google Patents
0.0 Dialkyl S (2 halogen 1 N phthahmidoathyl) thiophosphate, Ver drive for their production and pesticides containing themInfo
- Publication number
- DE1695181C DE1695181C DE19671695181 DE1695181A DE1695181C DE 1695181 C DE1695181 C DE 1695181C DE 19671695181 DE19671695181 DE 19671695181 DE 1695181 A DE1695181 A DE 1695181A DE 1695181 C DE1695181 C DE 1695181C
- Authority
- DE
- Germany
- Prior art keywords
- dialkyl
- thiophosphate
- halogen
- parts
- phthahmidoathyl
- 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.)
- Expired
Links
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 title claims description 7
- 229910052736 halogen Inorganic materials 0.000 title description 2
- 239000000575 pesticide Substances 0.000 title description 2
- 150000002367 halogens Chemical class 0.000 title 1
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XKJCHHZQLQNZHY-UHFFFAOYSA-N Phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 229910052801 chlorine Chemical group 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SULWMEGSVQCTSK-UHFFFAOYSA-N diethyl hydrogen phosphite Chemical compound CCOP(O)OCC SULWMEGSVQCTSK-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000749 insecticidal Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LHUFWKZQQCSODB-UHFFFAOYSA-N 2-(1,2-dibromoethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C(Br)CBr)C(=O)C2=C1 LHUFWKZQQCSODB-UHFFFAOYSA-N 0.000 description 1
- 241000305186 Persectania ewingii Species 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000855 fungicidal Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000002363 herbicidal Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
Description
CH1XCH 1 X
in welcher R Methyl oder Äthyl und X Brom oder Chlor ist.in which R is methyl or ethyl and X is bromine or chlorine.
2. Verfahren zur Herstellung der O,O-Dialkyl-S-{2-halogen-1 -N-phthalimidoäthyl)-thiophosphaten gemäß Anspruch 1, dadurch gekennzeichnet, daß man in üblicher Weise N-(l,2-dihalogenäthyl)-phthalimid mit einem Salz einer Dialkylthiophosphorsäure umsetzt.2. Process for the preparation of the O, O-dialkyl-S- {2-halo-1 -N-phthalimidoethyl) thiophosphates according to claim 1, characterized in that that in the usual way N- (l, 2-dihaloethyl) phthalimide with a salt of a dialkylthiophosphoric acid implements.
3. Schädlingsbekämpfungsmittel, gekennzeichnet durch einen Gehalt an einem 0,0-Dialkyl-S - (2 - halogen -1 - N - phthalimidoäthy 1) - thiophosphat gemäß Anspruch 1.3. Pesticides, characterized in that they contain a 0,0-dialkyl-S - (2 - halogen -1 - N - phthalimidoethy 1) - thiophosphate according to claim 1.
Die folgender Beispiele erläutern das Verfahren der Herstellung der erfindungsgemäßen Verbindungen und ihre Anwendungsweise. Alle Angaben über Teile und Prozentsätze sind Gewichtsangaben.The following examples illustrate the process of preparing the compounds of the invention and their mode of application. All parts and percentages are given by weight.
Durch Zugabe von 20,7 Teilen Diäthylhydrogenphosphit zu einer Lösung von Natriumäthoxyd. dit aus 3 5 Teilen Natrium in 74 Teilen Äthanol hergestellt wurde. 15minutiges Rühren, schrittweises Zusetzen von 4,8 Teilen Schwefel (gepulvert} bei 30 C und weiteres 15minutiges Rühren wurde eine Lösung des Natriumsalzes von O,O-Däthylthiophosphorsäure hergestellt. Zu dieser Lösung wurden 24,4 Teile N-( 1.2-dichloräthyl)-phthalimid zugesetzt. un;i die Mischung wurde 48 Stunden lang bei 24° C, schließlich 5 Stunden lang bei 50 bis 6O0C geiührt. Das ausgeschiedene Natriumchlorid wurde durch Filtration entfernt und der als Lösungsmittel eingesetzte Alkohol abdestilliert. Der Rückstand wurde in Benzol aufgenommen und mit 5%iger wäßriger Natriumbicarbonatlösung, mit 10%iger Salzsäure und dann mit Wasser gewaschen. Nach Trocknung wurde das Benzol entfernt, und es fielen 31,2 Teile eines gelben Öles an, das sich als O,O-Diäthyl-S-[2-chlor-l-(N-phthalimid)-äthyl]-thiophosphat erwies.By adding 20.7 parts of diethyl hydrogen phosphite to a solution of sodium ethoxide. dit was prepared from 35 parts of sodium in 74 parts of ethanol. Stirring for 15 minutes, gradually adding 4.8 parts of sulfur (powdered) at 30 ° C. and stirring for a further 15 minutes, a solution of the sodium salt of O, O-diethylthiophosphoric acid was prepared. 24.4 parts of N- (1,2-dichloroethyl) - . phthalimide added un i the mixture for 48 hours at 24 ° C, finally geiührt for 5 hours at 50 to 6O 0 C the precipitated sodium chloride was removed by distillation removed by filtration and the alcohol used as the solvent the residue was taken up in benzene.. and washed with 5% aqueous sodium bicarbonate solution, with 10% hydrochloric acid and then with water.After drying, the benzene was removed, and 31.2 parts of a yellow oil were obtained, which was found to be O, O-diethyl-S- [ 2-chloro-1- (N-phthalimide) ethyl] thiophosphate proved.
Analyse:Analysis:
7,1% Phosphor (theor. 8,2%);
9,8% Schwefel (theor. 8,5%).7.1% phosphorus (theor. 8.2%);
9.8% sulfur (theor. 8.5%).
N-CH-S-P(OR)2 N-CH-SP (OR) 2
Die vorliegende Erfindung betrifft O,O-Dialkyl-SL(2-halogen-1 -N-phthalimidoäthyl)-thiophosphate der FormelThe present invention relates to O, O-dialkyl-S L (2-halogen-1-N-phthalimidoethyl) thiophosphates of the formula
5050
in welcher R Methyl oder Äthyl und X Brom oder Chlor ist.in which R is methyl or ethyl and X is bromine or chlorine.
Gemäß der vorliegenden Erfindung werden die O.O-Dialkyl-S-P-halogen-l-iN-phthalimidi-äthyl]-thiophosphate in an sich bekannter Weise durch Umsetzung von N-(l,2-dihalogenäthyl)-phthalimid mit einem Salz einer 0,0-Dialkylthiophosphorsäure hergestellt. According to the present invention, the O.O-dialkyl-S-P-halogen-1-iN-phthalimidi-ethyl] thiophosphates in a manner known per se by reacting N- (l, 2-dihalogenoethyl) phthalimide with a salt of 0,0-dialkylthiophosphoric acid.
Die erfindungsgemäßen Verbindungen können in den üblichen Dispersionen angewendet werden. Geeignete Dispergierungs- und Ernulgierungsmittel sind z. B. in Chemistry of Insecticides, Fungicides and Herbicides, Sec. Ed. (1948) angeführt. Eine übliche wäßrige Dispersion besteht z. B. aus etwa 10 bis 90% der aktiven Verbindung, etwa 0,5 bis 10% Dispergierungsmittel und 0 bis 90% inerten Verdünnungsmittel. The compounds according to the invention can be used in the customary dispersions. Suitable Dispersing and emulsifying agents are e.g. B. in Chemistry of Insecticides, Fungicides and Herbicides, Sec. Ed. (1948) cited. A common aqueous dispersion consists, for. B. from about 10 to 90% of the active compound, about 0.5 to 10% dispersant and 0 to 90% inert diluent.
Das Triäthylaminsalz von O,O-Diäthyl-S-(hydrogenthiophosphorsäuri) wurde hergestellt, indem man 5,05 Teile Triäthylamin in 3,9 Teilen Acetonitril tropfenweise zu 6,9 Teilen Diäthylhydrogenphosphit in 7,8 Teilen Acetonitril zufügte, dann 1,6 Teile gepulverten Schwefel zusetzte und das Reaktionsgemisch unter Einhaltung einer Temperatur von 25 bis 35° C rührte. Nach 30 Minuten wurden 8,32 Teile N-(l,2-dibromäthyl)-phthalimid unter Rühren bei etwa 24° C zugefügt, und nach 30 Minuten wurde die Mischung 1 Stunde lang bei 50° C erhitzt. Die erhaltene Reaktionsmischung wurde in Wasser gegossen, mit Benzol extrahiert, und der Benzolextrakt wurde mit 5%iger Natriumbicprbonatlösung und dann mit Wasser gewaschen. Die Benzollösung wurde getrocknet und die Lösungsmittel unter vermindertem Druck bei einer Temperatur bis zu 6O0C abdestilliert. Das gebildete O,O-Diäthyl-S-[2-brom-l-(N-phthalimid)-äthyl]-thiophosphat wurde als eine zähe dunkelgelbe Flüssigkeit in einer Menge von 8,9 Teilen erhalten.The triethylamine salt of O, O-diethyl-S- (hydrogen thiophosphoric acid) was prepared by adding 5.05 parts of triethylamine in 3.9 parts of acetonitrile dropwise to 6.9 parts of diethyl hydrogen phosphite in 7.8 parts of acetonitrile, then 1.6 parts powdered sulfur was added and the reaction mixture was stirred while maintaining a temperature of 25 to 35.degree. After 30 minutes, 8.32 parts of N- (1,2-dibromoethyl) phthalimide were added with stirring at about 24 ° C, and after 30 minutes the mixture was heated at 50 ° C for 1 hour. The obtained reaction mixture was poured into water, extracted with benzene, and the benzene extract was washed with 5% sodium bicarbonate solution and then with water. The benzene solution was dried and the solvent was distilled off under reduced pressure at a temperature up to 6O 0 C. The formed O, O-diethyl-S- [2-bromo-1- (N-phthalimide) ethyl] thiophosphate was obtained as a viscous dark yellow liquid in an amount of 8.9 parts.
Analyse:Analysis:
17,5% Brom (theor. 19,0%);
9,5% Schwefel (theor. 7,6%).17.5% bromine (theor. 19.0%);
9.5% sulfur (theor. 7.6%).
Offensichtlich enthielt das Produkt eine geringe Menge gelösten elementaren Schwefels. Auf Grund des Infrarotspektrums (es zeigten sich Banden bei 5,6, 5,8, 9,5 bis 10 und 10,2 bis 10,4 πΐμ) enthielt das Produkt die Imidgruppe und die = P(OC2H5)2-Gruppe. Apparently the product contained a small amount of dissolved elemental sulfur. Based on the infrared spectrum (there were bands at 5.6, 5.8, 9.5 to 10 and 10.2 to 10.4 πΐμ) the product contained the imide group and the = P (OC 2 H 5 ) 2 - Group.
VergleichsbeispielComparative example
Da die erfindungsgemäßen Stoffe eng verwandt sind mit dem als Handelsprodukt bekannten Insektizid, welches die StrukturformelSince the substances according to the invention are closely related to the insecticide known as a commercial product, which is the structural formula
Verbindung'lConnection'l
0Zo Abtötunj; der 0 zo kill; the
Larven desLarvae of
Soulhern ArmySoulhern Army
Wurms bei 0.0250OWorms at 0.025 0 O
Anwendungs-Application
konzenlralionconcentraion
N-CH2-SP-(OCHj)2 N-CH 2 -SP- (OCHj) 2
besitzt (mit R N — ist in der Formel die Phthal-(with R N - in the formula the phthalic
imidogruppe angedeutet), wurden Vergleichsversache mit einer dem Imidan entsprechenden Verbindung durchgerührt.imido group indicated), comparative experiments were made with a compound corresponding to the imidane stirred.
Aus der nachstehenden Tabelle geht hervor, daß eine Emulsion mit einem Wirkstoffgehalt von 0,025% eingesetzt gegen Larven des Southern Army Wurms im Falle d -r erfindungsgemäßen Verbindungen eine 73- bzw. 63% ige Abtötung, im Falle der Vergleichsverbindung dagegen nur eine 27% ige Abtötung erbrachte. The table below shows that an emulsion with an active ingredient content of 0.025% used against larvae of the Southern Army worm in the case of the compounds according to the invention a 73- or 63% kill, in the case of the comparison compound, on the other hand, only resulted in a 27% kill.
N-CH — SP-(OC2H5^N-CH - SP- (OC 2 H 5 ^
N-CH — SP-(OC2Hs)2 N-CH - SP- (OC 2 Hs) 2
7373
6363
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53573566 | 1966-03-21 | ||
| US535735A US3355353A (en) | 1966-03-21 | 1966-03-21 | Omicron, omicron-dialkyl s-[2-halo-1-(nu-phthalimido) ethyl] phosphorodithioates and phosphorothioates as insecticides |
| DEH0062091 | 1967-03-10 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1695181A1 DE1695181A1 (en) | 1970-12-10 |
| DE1695181B2 DE1695181B2 (en) | 1973-01-18 |
| DE1695181C true DE1695181C (en) | 1973-08-23 |
Family
ID=
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