DE2607176A1 - THIONO or THIONOTHIOL PHOSPHORUS AND THIONOPHOSPHONIC ACID ESTER - Google Patents
THIONO or THIONOTHIOL PHOSPHORUS AND THIONOPHOSPHONIC ACID ESTERInfo
- Publication number
- DE2607176A1 DE2607176A1 DE19762607176 DE2607176A DE2607176A1 DE 2607176 A1 DE2607176 A1 DE 2607176A1 DE 19762607176 DE19762607176 DE 19762607176 DE 2607176 A DE2607176 A DE 2607176A DE 2607176 A1 DE2607176 A1 DE 2607176A1
- Authority
- DE
- Germany
- Prior art keywords
- dichloro
- thionothiol
- carbon atoms
- cyanophenyl
- thiono
- 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.)
- Withdrawn
Links
- 150000002148 esters Chemical class 0.000 title claims description 6
- 239000002253 acid Substances 0.000 title claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title 1
- 229910052698 phosphorus Inorganic materials 0.000 title 1
- 239000011574 phosphorus Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 20
- LIDUSYSXQFAHHK-UHFFFAOYSA-N 2,5-dichloro-4-hydroxybenzonitrile Chemical compound OC1=CC(Cl)=C(C#N)C=C1Cl LIDUSYSXQFAHHK-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 150000004707 phenolate Chemical class 0.000 claims description 2
- 229940031826 phenolate Drugs 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 241000607479 Yersinia pestis Species 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- -1 2,5-dichloro-4-cyanophenyl Chemical group 0.000 description 11
- 239000004480 active ingredient Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000238660 Blattidae Species 0.000 description 1
- GJPYESGAIZJIGC-UHFFFAOYSA-N C(C)(C)[ClH]P(=S)(C)Cl Chemical compound C(C)(C)[ClH]P(=S)(C)Cl GJPYESGAIZJIGC-UHFFFAOYSA-N 0.000 description 1
- QXHSLSJFHFRLTN-UHFFFAOYSA-N C(C)[ClH]P(=S)(C1=CC=CC=C1)Cl Chemical compound C(C)[ClH]P(=S)(C1=CC=CC=C1)Cl QXHSLSJFHFRLTN-UHFFFAOYSA-N 0.000 description 1
- DHNJJLGNNQXPRZ-UHFFFAOYSA-N C(C)[ClH]P(=S)(Cl)[ClH]CC Chemical compound C(C)[ClH]P(=S)(Cl)[ClH]CC DHNJJLGNNQXPRZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- 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
- A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
- A01N57/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing aromatic 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
- C07F9/4084—Esters with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Die Erfindung betrifft Thiono- bzw. Thionothiolphosphor- sowie Thionophosphonsäureester der Formel
ihre Verwendung in Schädlingsbekämpfungsmitteln und Verfahren zu ihrer Herstellung.their use in pesticides and processes for their manufacture.
In der Formel I und im folgenden haben die Substituenten R[tief]1 und R[tief]2 die nachstehende Bedeutung:In formula I and in the following, the substituents R [deep] 1 and R [deep] 2 have the following meanings:
R[tief]1 bedeutet einen Alkylrest mit 1 - 3 Kohlenstoffatomen;R [deep] 1 denotes an alkyl radical with 1 to 3 carbon atoms;
R[tief]2 bezeichnet einen Alkylrest mit 1 - 3 Kohlenstoffatomen, einen Phenylrest, einen Alkoxyrest mit 1 - 3 Kohlenstoffatomen oder einen Alkylthiorest mit 1 - 4 Kohlenstoffatomen.R [deep] 2 denotes an alkyl group with 1 - 3 carbon atoms, a phenyl group, an alkoxy group with 1 - 3 carbon atoms or an alkylthio group with 1 - 4 carbon atoms.
Hervorzuheben sind diejenigen Verbindungen der Formel I, in denen die Alkyl-, Alkoxy- und Alkylmercaptogruppen 1 bis
<NichtLesbar>
To be emphasized are those compounds of the formula I in which the alkyl, alkoxy and alkyl mercapto groups 1 to
<notreadable>
C-Atome enthalten.Contain carbon atoms.
Die Verbindungen der Formel I erhält man nach üblichen Methoden durch Umsetzung eines Phosphorsäurechlorids der Formel
mit 2,5-Dichlor-4-cyanophenol
Die Umsetzung erfolgt in einem geeigneten organischen Lösungsmittel, z.B. Toluol, Dioxan, Tetrahydrofuran, Methyläthylketon oder auch in Wasser bei Temperaturen von etwa
<NichtLesbar>
bis 90°C. Die geeigneten Phenolate können sich z.B. von Alkalibasen oder von organischen Basen, wie Triäthylamin, Äthylpiperidin, Trimethylamin, ableiten.The reaction takes place in a suitable organic solvent, for example toluene, dioxane, tetrahydrofuran, methyl ethyl ketone or in water at temperatures of about
<notreadable>
up to 90 ° C. The suitable phenates can be derived, for example, from alkali bases or from organic bases such as triethylamine, ethylpiperidine, trimethylamine.
Die rohen Ester werden zur Reinigung in einem geeigneten organischen Lösungsmittel aufgenommen und die Lösung mit verdünnter Natronlauge und Wasser gewaschen, getrocknet und gegebenenfalls mit Aktivkohle behandelt und eingeengt.For purification, the crude esters are taken up in a suitable organic solvent and the solution is washed with dilute sodium hydroxide solution and water, dried and, if necessary, treated with activated charcoal and concentrated.
Die neuen Verbindungen bleiben als farblose bis hellgelbe Öle von genügender Reinheit zurück. Teilweise sind die Ester kristallin. Im allgemeinen sind die Verbindungen im Hochvakuum ohne merkliche Zersetzung destillierbar.The new compounds remain as colorless to light yellow oils of sufficient purity. Some of the esters are crystalline. In general, the compounds can be distilled in a high vacuum without noticeable decomposition.
Soweit die Ausgangsstoffe noch nicht beschrieben wurden, können sie nach an sich bekannten Verfahren gewonnen werden. Die Ester der Formel I können als Wirkstoffe in Schädlingsbekämpfungsmitteln verwandt werden.If the starting materials have not yet been described, they can be obtained by methods known per se. The esters of the formula I can be used as active ingredients in pesticides.
Sie wirken stark insekticid und akarizid, beispielsweise auch gegen resistente Spinnmilben, außerdem haben sie eine fungizide Wirkung, insbesondere gegen echten Mehltau.They have a strong insecticidal and acaricidal effect, for example also against resistant spider mites, and they also have a fungicidal effect, especially against powdery mildew.
Die gute Wirksamkeit der neuen Verbindungen zeigt sich z.B. beim Vergleich zwischen dem Handelsprodukt O,O-Diäthyl-O-(4-brom-2,5-dichlorphenyl)-thionophosphat (A) und der erfindungsgemäßen Verbindung O,O-Diäthyl-O-(2,5-dichlor-4-cyanophenyl)-thionophosphat (B) an orientalischen Schaben (Kontrolle nach 2 Tagen, Abtötung in %):The good effectiveness of the new compounds is shown, for example, in a comparison between the commercial product O, O-diethyl-O- (4-bromo-2,5-dichlorophenyl) thionophosphate (A) and the compound according to the invention O, O-diethyl-O- (2,5-dichloro-4-cyanophenyl) thionophosphate (B) on oriental cockroaches (control after 2 days, destruction in%):
Wirkstoff 0,6 ppm 1,0 ppm 2,5 ppmActive ingredient 0.6 ppm 1.0 ppm 2.5 ppm
______________________________________________________________________________________________________________________________________
A 0 10 30A 0 10 30
B 60 90 100B 60 90 100
Für die Anwendung werden die erfindungsgemäßen Verbindungen zu den üblichen Formulierungen verarbeitet, z.B. zu Emulsionen, Suspensionen, Streu- und Stäubemitteln. Die Anwendungskonzentrationen liegen im allgemeinen zwischen etwa 0,01 und 5 Gew.-%. Sie können jedoch auch höher gewählt werden, z.B. für die Anwendung der Wirkstoffe in ULV-Formulierungen, die bis zu etwa 90 Gew.-% Wirkstoff enthalten können.For use, the compounds according to the invention are processed into the customary formulations, e.g. into emulsions, suspensions, scattering agents and dusts. The use concentrations are generally between about 0.01 and 5% by weight. However, you can also go higher can be selected, e.g. for the use of the active ingredients in ULV formulations, which can contain up to about 90% by weight of active ingredient.
FormulierungsbeispieleFormulation examples
a) Emulsionskonzentratea) Emulsion concentrates
20 Gew.-Teile eines Wirkstoffs gemäß der Erfindung werden in 75 Gew.-Teilen Xylol gelöst und mit 5 Gew.-Teilen Nonylphenolpolyglycoläther versetzt. Diese Lösung wird für die Anwendung mit Wasser emulgiert. Der Wirkstoffgehalt der Emulsionen beträgt im allgemeinen zwischen 0,01 und 0,1 Gew.-%.20 parts by weight of an active ingredient according to the invention are dissolved in 75 parts by weight of xylene, and 5 parts by weight of nonylphenol polyglycol ether are added. This solution is emulsified with water for use. The active ingredient content of the emulsions is generally between 0.01 and 0.1% by weight.
b) Stäubemittelb) dust
2 Gew.-Teile O,O-Diäthyl-O-(2,5-dichlor-4-cyanophenyl)-thionophat werden auf 98 Gew.-Teile Kaolin aufgedüst und mit diesem homogen vermahlen.2 parts by weight of O, O-diethyl-O- (2,5-dichloro-4-cyanophenyl) thionophate are sprayed onto 98 parts by weight of kaolin and ground homogeneously with this.
c) Suspensionspulverc) suspension powder
25 Gew.-Teile eines erfindungsgemäßen Wirkstoffs werden auf 73 Gew.-Teile Kieselgur aufgedüst und nach Zusatz von 2 Teilen Natrium-naphthalinsulfonat homogen vermahlen. Für die Anwendung wird das erhaltene Suspensionspulver mit Wasser bis zur gewünschten Konzentration (vorzugsweise 0,01 - 0,1 Gew.-% Wirkstoff) vermischt.25 parts by weight of an active ingredient according to the invention are sprayed onto 73 parts by weight of kieselguhr and, after the addition of 2 parts of sodium naphthalenesulfonate, ground homogeneously. For use, the suspension powder obtained is mixed with water up to the desired concentration (preferably 0.01-0.1% by weight of active ingredient).
Die Herstellung der erfindungsgemäßen Verbindungen ist in den folgenden Beispielen näher erläutert.The preparation of the compounds according to the invention is explained in more detail in the following examples.
Beispiel 1example 1
O,O-Diäthyl-O-(2,5-dichlor-4-cyanophenyl)-thionophosphat
<NichtLesbar>
g 2,5-Dichlor-4-cyanophenol wird in 100 ml Tetrahydrofuran gelöst und mit 14,0 g Kaliumcarbonat versetzt. Hierbei bildet sich das Kaliumsalz des Phenols. Unter Rühren wird bei 50 - 60°C langsam O,O-Diäthyl-thionophosphorsäurechlorid eingetropft und anschließend 3 Stunden im Wasserbad unter Rückfluß erhitzt. Die Reaktionslösung wird filtriert und eingeengt. Der Rückstand wird in 1,2-Dichloräthan gelöst und mit verdünnter Natronlauge ausgeschüttelt. Nach dem Trocknen der Dichloräthanlösung mit Natriumsulfat wird filtriert und das Lösungsmittel im Vakuum vollständig entfernt.O, O-diethyl O- (2,5-dichloro-4-cyanophenyl) thionophosphate
<notreadable>
g of 2,5-dichloro-4-cyanophenol is dissolved in 100 ml of tetrahydrofuran and mixed with 14.0 g of potassium carbonate. This forms the potassium salt of phenol. O, O-diethyl-thionophosphoric acid chloride is slowly added dropwise at 50-60 ° C. with stirring and then refluxed for 3 hours in a water bath. The reaction solution is filtered and concentrated. The residue is dissolved in 1,2-dichloroethane and extracted with dilute sodium hydroxide solution. After the dichloroethane solution has been dried with sodium sulfate, it is filtered and the solvent is completely removed in vacuo.
Ausbeute 35,5 g (98,5 % d. Th.).Yield 35.5 g (98.5% of theory).
Die Substanz ist dünnschichtchromatographisch einheitlich. Aus einer Mischung von Cyclohexan und Methanol kann die Verbindung kristallin erhalten werden; Fp. 58°C.The substance is uniform according to thin-layer chromatography. The compound can be obtained in crystalline form from a mixture of cyclohexane and methanol; M.p. 58 ° C.
Beispiel 2Example 2
O,O-Diäthyl-O-(2,5-dichlor-4-cyanophenyl)-thionophosphatO, O-diethyl O- (2,5-dichloro-4-cyanophenyl) thionophosphate
132 g (0,7 Mol) 2,5-Dichlor-4-cyanophenol werden in 200 ml (0,75 Mol) 15 %iger wäßriger Natronlauge gelöst, mit 150 ml Dichloräthan versetzt und bei einer Temperatur von 60 - 65°C unter kräftigem Rühren mit 170 g O,O-Diäthyl-thionophosphorsäurechlorid umgesetzt. Nach etwa 1,5 Stunden ist die Reaktion beendet. Die organische Phase wird abgetrennt und mit 1 n Natronlauge und Wasser gewaschen. Nach dem Abdestillieren des Lösungsmittels wird das überschüssige Phosphorsäurechlorid bei ca. 1 Torr abgezogen. Die Ausbeute beträgt 228 g (96 % d. Th.).132 g (0.7 mol) of 2,5-dichloro-4-cyanophenol are dissolved in 200 ml (0.75 mol) of 15% aqueous sodium hydroxide solution, mixed with 150 ml of dichloroethane and at a temperature of 60-65 ° C below vigorous stirring with 170 g of O, O-diethyl thionophosphoric acid chloride. The reaction has ended after about 1.5 hours. The organic phase is separated off and washed with 1N sodium hydroxide solution and water. After the solvent has been distilled off, the excess phosphoric acid chloride is stripped off at about 1 Torr. The yield is 228 g (96% of theory).
Die Verbindung wird entsprechend Beispiel 1 zur Kristallisation gebracht, Fp. 58°C.The compound is crystallized as in Example 1, melting point 58.degree.
Beispiel 3Example 3
O,O-Dimethyl-O-(2,5-dichlor-4-cyanophenyl)-thionophosphatO, O-dimethyl-O- (2,5-dichloro-4-cyanophenyl) thionophosphate
Die Verbindung wird entsprechend Beispiel 1 oder Beispiel 2 aus O,O-Dimethyl-thionophosphorsäurechlorid und 2,5-Dichlor-4-cyanophenol hergestellt.The compound is prepared according to Example 1 or Example 2 from O, O-dimethyl-thionophosphoric acid chloride and 2,5-dichloro-4-cyanophenol.
Brechungsindex: n[hoch]24[tief]D 1,6032; Ausbeute: 82 % d. Th.Refractive index: n [high] 24 [low] D 1.6032; Yield: 82% of theory Th.
Beispiel 4Example 4
O,O-Di-n-propyl-O-(2,5-dichlor-4-cyanophenyl)-thionophosphatO, O-di-n-propyl-O- (2,5-dichloro-4-cyanophenyl) thionophosphate
Analog Beispiel 1 wird durch Umsetzung von O,O-Di-n-propyl-thionophosphorsäurechlorid mit 2,5-Dichlor-4-cyanophenol die Titelverbindung hergestellt.Analogously to Example 1, the title compound is prepared by reacting O, O-di-n-propyl-thionophosphoric acid chloride with 2,5-dichloro-4-cyanophenol.
Brechungsindex: n[hoch]22[tief]D 1,5834; Ausbeute: 81 % d. Th.Refractive index: n [high] 22 [low] D 1.5834; Yield: 81% of theory Th.
Beispiel 5Example 5
O-Äthyl-O-(2,5-dichlor-4-cyanophenyl)-äthylthionophosphonatO-ethyl-O- (2,5-dichloro-4-cyanophenyl) -ethylthionophosphonate
Die Titelverbindung wird entsprechend Beispiel 1 oder Beispiel 2 aus 2,5-Dichlor-4-cyanophenol und O-Äthyl-äthyl-thionophosphorsäurechlorid hergestellt.The title compound is prepared according to Example 1 or Example 2 from 2,5-dichloro-4-cyanophenol and O-ethyl-ethyl-thionophosphoric acid chloride.
Brechungsindex: n[hoch]24[tief]D 1,5983; Ausbeute: 74 % d. Th.Refractive index: n [high] 24 [low] D 1.5983; Yield: 74% of theory Th.
Beispiel 6Example 6
O-Isopropyl-O-(2,5-dichlor-4-cyanophenyl)-methylthionophosphonatO-Isopropyl O- (2,5-dichloro-4-cyanophenyl) methylthionophosphonate
Analog Beispiel 1 oder Beispiel 2 erhält man aus 2,5-Dichlor-4-cyanophenol und O-Isopropyl-methylthionophosphonsäurechlorid die Titelverbindung.The title compound is obtained analogously to Example 1 or Example 2 from 2,5-dichloro-4-cyanophenol and O-isopropyl-methylthionophosphonic acid chloride.
Brechungsindex: n[hoch]22[tief]D 1,6023; Ausbeute: 78 % d. Th.Refractive index: n [high] 22 [low] D 1.6023; Yield: 78% of theory Th.
Beispiel 7Example 7
O-Äthyl-O-(2,5-dichlor-4-cyanophenyl)-phenylthionophosphonatO-ethyl O- (2,5-dichloro-4-cyanophenyl) phenylthionophosphonate
Die Titelverbindung wird analog Beispiel 1 oder 2 aus O-Äthyl-phenylthionophosphonsäurechlorid und 2,5-Dichlor-4-cyanophenol erhalten.The title compound is obtained analogously to Example 1 or 2 from O-ethyl-phenylthionophosphonic acid chloride and 2,5-dichloro-4-cyanophenol.
Brechungsindex: n[hoch]23[tief]D 1,5221; Ausbeute: 87 % d. Th.Refractive index: n [high] 23 [low] D 1.5221; Yield: 87% of theory Th.
Beispiel 8Example 8
O-Äthyl-S-n-propyl-O-(2,5-dichlor-4-cyanophenyl)-thionothiolphosphatO-ethyl-S-n-propyl-O- (2,5-dichloro-4-cyanophenyl) thionothiol phosphate
Die Titelverbindung wird entsprechend Beispiel 1 durch Umsetzung von O-Äthyl-S-n-propyl-thionothiolphosphorsäurechlorid mit 2,5-dichlor-4-cyanophenol erhalten.The title compound is obtained according to Example 1 by reacting O-ethyl-S-n-propyl-thionothiolphosphoric acid chloride with 2,5-dichloro-4-cyanophenol.
Brechungsindex: n[hoch]25[tief]D 1,5703; Ausbeute: 78 % d. Th.Refractive index: n [high] 25 [low] D 1.5703; Yield: 78% of theory Th.
Entsprechend den obigen Beispielen können ferner erhalten werden:According to the above examples, the following can also be obtained:
O,S-Dimethyl-O-(2,5-dichlor-4-cyanophenyl)-thionothiolphosphat;O, S-dimethyl-O- (2,5-dichloro-4-cyanophenyl) thionothiol phosphate;
O,S-Diäthyl-O-(2,5-dichlor-4-cyanophenyl)-thionothiolphosphat;O, S-diethyl O- (2,5-dichloro-4-cyanophenyl) thionothiol phosphate;
O,S-Diisopropyl-O-(2,5-dichlor-4-cyanophenyl)-thionothiolphosphat;O, S-diisopropyl-O- (2,5-dichloro-4-cyanophenyl) thionothiol phosphate;
O-Äthyl-S-n-isopropyl-O-(2,5-dichlor-4-cyanophenyl)-thionothiolphosphat;O-ethyl-S-n-isopropyl-O- (2,5-dichloro-4-cyanophenyl) thionothiol phosphate;
O-Äthyl-S-n-butyl-O-(2,5-dichlor-4-cyanophenyl)-thionothiolphosphat;O-ethyl-S-n-butyl-O- (2,5-dichloro-4-cyanophenyl) thionothiol phosphate;
O-Äthyl-S-tert.-butyl-O-(2,5-dichlor-4-cyanophenyl)-thionothiolphosphat.O-ethyl-S-tert-butyl-O- (2,5-dichloro-4-cyanophenyl) thionothiol phosphate.
Claims (4)
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762607176 DE2607176A1 (en) | 1976-02-21 | 1976-02-21 | THIONO or THIONOTHIOL PHOSPHORUS AND THIONOPHOSPHONIC ACID ESTER |
| CH198477A CH627476A5 (en) | 1976-02-21 | 1977-02-17 | Pesticide |
| NL7701731A NL7701731A (en) | 1976-02-21 | 1977-02-18 | PROCESS FOR PREPARING NEW THIONO RESP. THIONOTHIOLPHOSPHORIC BOTH AND THIONOPHOSPHONIC ACID ESTERS. |
| JP1701377A JPS52102257A (en) | 1976-02-21 | 1977-02-18 | Thiono or thionothiol phosphate and thionophosphonate esters and process for preparing same |
| GB6983/77A GB1530112A (en) | 1976-02-21 | 1977-02-18 | Thionophosphoric and thionophosphonic acid esters having pesticidal activity |
| DK70577A DK141937C (en) | 1976-02-21 | 1977-02-18 | THIONOPHOSPHORIC ACID ESTERS FOR USE IN INSECTICIDES |
| IT48124/77A IT1083471B (en) | 1976-02-21 | 1977-02-18 | THYROPHOSPHORIC ACID ESTERS |
| IL51491A IL51491A (en) | 1976-02-21 | 1977-02-18 | 2,5-dichloro-4-cyanophenyl esters of thionophosphoric acid,their preparation and insecticidal,acaricidal and fungicidal compositions containing them |
| BE175103A BE851629A (en) | 1976-02-21 | 1977-02-18 | ESTERS OF THIONO- OR THIONOTHIOPHOSPHORIC ACIDS AS WELL AS THIONOPHOSPHONIC ACIDS |
| ES456104A ES456104A1 (en) | 1976-02-21 | 1977-02-19 | Thionophosphoric and thionophosphonic acid esters having pesticidal activity |
| FR7704959A FR2341588A1 (en) | 1976-02-21 | 1977-02-21 | ESTERS OF THIONO- OR THIONOTHIOPHOSPHORIC ACIDS AS WELL AS THIONOPHOSPHONIC ACIDS, THEIR PREPARATION AND THEIR USE AS AGENTS FOR THE CONTROL OF PARASITES |
| US05/824,414 US4150124A (en) | 1976-02-21 | 1977-08-15 | 2,5-Dichloro-4-cyano-phenyl esters of thionophosphoric, thionothiolphosphoric and thionophosphonic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762607176 DE2607176A1 (en) | 1976-02-21 | 1976-02-21 | THIONO or THIONOTHIOL PHOSPHORUS AND THIONOPHOSPHONIC ACID ESTER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2607176A1 true DE2607176A1 (en) | 1977-09-01 |
Family
ID=5970586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19762607176 Withdrawn DE2607176A1 (en) | 1976-02-21 | 1976-02-21 | THIONO or THIONOTHIOL PHOSPHORUS AND THIONOPHOSPHONIC ACID ESTER |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS52102257A (en) |
| BE (1) | BE851629A (en) |
| CH (1) | CH627476A5 (en) |
| DE (1) | DE2607176A1 (en) |
| DK (1) | DK141937C (en) |
| ES (1) | ES456104A1 (en) |
| FR (1) | FR2341588A1 (en) |
| GB (1) | GB1530112A (en) |
| IL (1) | IL51491A (en) |
| IT (1) | IT1083471B (en) |
| NL (1) | NL7701731A (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1281570A (en) * | 1960-03-07 | 1962-01-12 | Yashima Kagaku Kogyo Kabushiki | New phosphoric and thio-phosphoric esters, their preparation process and insecticides containing them |
| NL7310390A (en) * | 1972-02-07 | 1975-01-28 | Celamerck Gmbh & Co Kg | Thiophosphoric - and thiophosphonic esters - by transesterification using a weak base as catalyst |
| FR2239475A2 (en) * | 1972-02-07 | 1975-02-28 | Celamerck Gmbh & Co Kg | Thiophosphoric - and thiophosphonic esters - by transesterification using a weak base as catalyst |
| AT321943B (en) * | 1972-02-07 | 1975-04-25 | Oicelamerck Gmbh & Co Kg | Process for the preparation of thionophosphorus or thionophosphonic acid esters |
-
1976
- 1976-02-21 DE DE19762607176 patent/DE2607176A1/en not_active Withdrawn
-
1977
- 1977-02-17 CH CH198477A patent/CH627476A5/en not_active IP Right Cessation
- 1977-02-18 IL IL51491A patent/IL51491A/en unknown
- 1977-02-18 DK DK70577A patent/DK141937C/en active
- 1977-02-18 JP JP1701377A patent/JPS52102257A/en active Pending
- 1977-02-18 BE BE175103A patent/BE851629A/en unknown
- 1977-02-18 GB GB6983/77A patent/GB1530112A/en not_active Expired
- 1977-02-18 NL NL7701731A patent/NL7701731A/en not_active Application Discontinuation
- 1977-02-18 IT IT48124/77A patent/IT1083471B/en active
- 1977-02-19 ES ES456104A patent/ES456104A1/en not_active Expired
- 1977-02-21 FR FR7704959A patent/FR2341588A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL7701731A (en) | 1977-08-23 |
| GB1530112A (en) | 1978-10-25 |
| DK70577A (en) | 1977-08-22 |
| ES456104A1 (en) | 1978-02-01 |
| IL51491A (en) | 1980-12-31 |
| BE851629A (en) | 1977-08-18 |
| DK141937B (en) | 1980-07-21 |
| FR2341588A1 (en) | 1977-09-16 |
| DK141937C (en) | 1980-12-01 |
| CH627476A5 (en) | 1982-01-15 |
| IL51491A0 (en) | 1977-04-29 |
| IT1083471B (en) | 1985-05-21 |
| JPS52102257A (en) | 1977-08-27 |
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| 8139 | Disposal/non-payment of the annual fee |