DE1226584B - Process for the preparation of thiophosphonic acid esters - Google Patents
Process for the preparation of thiophosphonic acid estersInfo
- Publication number
- DE1226584B DE1226584B DEF32583A DEF0032583A DE1226584B DE 1226584 B DE1226584 B DE 1226584B DE F32583 A DEF32583 A DE F32583A DE F0032583 A DEF0032583 A DE F0032583A DE 1226584 B DE1226584 B DE 1226584B
- Authority
- DE
- Germany
- Prior art keywords
- acid esters
- thiophosphonic acid
- preparation
- mol
- general formula
- 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
- 150000002148 esters Chemical class 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 11
- 239000002253 acid Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 241001454295 Tetranychidae Species 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- FTWDNQJEZZKJBW-UHFFFAOYSA-N 3-(bromomethyl)-2H-1,3-benzothiazole 1-oxide Chemical compound BrCN1CS(C2=C1C=CC=C2)=O FTWDNQJEZZKJBW-UHFFFAOYSA-N 0.000 description 6
- 241001124076 Aphididae Species 0.000 description 6
- 241000700159 Rattus Species 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 241000256113 Culicidae Species 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 241000238876 Acari Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- SCUBQKOBYMMETC-UHFFFAOYSA-N ethoxy-(3-ethyl-1-sulfanylidenethiophen-2-yl)phosphinic acid Chemical compound C(C)OP(=O)(O)C=1S(C=CC1CC)=S SCUBQKOBYMMETC-UHFFFAOYSA-N 0.000 description 2
- MLMQBNCHQYBBQQ-UHFFFAOYSA-N ethoxy-(3-methyl-1-sulfanylidenethiophen-2-yl)phosphinic acid Chemical compound C(C)OP(O)(=O)C=1S(C=CC1C)=S MLMQBNCHQYBBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- BXQNSPXDWSNUKE-UHFFFAOYSA-N 1,3-benzothiazole 1-oxide Chemical compound C1=CC=C2S(=O)C=NC2=C1 BXQNSPXDWSNUKE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CNXCABRTRPRYPR-UHFFFAOYSA-N 3-(bromomethyl)-1,3-benzoxazol-2-one Chemical compound C1=CC=C2OC(=O)N(CBr)C2=C1 CNXCABRTRPRYPR-UHFFFAOYSA-N 0.000 description 1
- FOHRCMUANUUOIL-UHFFFAOYSA-N 3-(hydroxymethyl)-1,3-benzoxazol-2-one Chemical class C1=CC=C2OC(=O)N(CO)C2=C1 FOHRCMUANUUOIL-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- ASSKVPFEZFQQNQ-UHFFFAOYSA-N Benzoxazolone Natural products C1=CC=C2OC(O)=NC2=C1 ASSKVPFEZFQQNQ-UHFFFAOYSA-N 0.000 description 1
- JAUUTXCDYWRITE-UHFFFAOYSA-N C(C)OP(=O)(O)C=1SC=CC1C Chemical compound C(C)OP(=O)(O)C=1SC=CC1C JAUUTXCDYWRITE-UHFFFAOYSA-N 0.000 description 1
- BPFSFNIQPNIIQH-UHFFFAOYSA-N CC(C)C1=C(S(=S)C=C1)P(=O)(O)O Chemical compound CC(C)C1=C(S(=S)C=C1)P(=O)(O)O BPFSFNIQPNIIQH-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000254179 Sitophilus granarius Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 231100000162 fungitoxic Toxicity 0.000 description 1
- 230000002464 fungitoxic effect Effects 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FLQUDUCNBDGCRI-UHFFFAOYSA-N hydroxy-sulfanyl-sulfidophosphanium Chemical class SP(S)=O FLQUDUCNBDGCRI-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000194 ovacidal Toxicity 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000001665 trituration Methods 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
- C07F9/65324—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6539—Five-membered rings
- C07F9/6541—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung von Thiophosphonsäureestern Die Erfindung betrifft ein Verfahren zur Ererstellung von Thiophosphonsäureestern der allgemeinen Formel in der Ri und R2 niedermolekulare Alkylreste, X, und X2 Sauerstoff :oder Schwefelatome und Y ein Wasserstoff= oder Halogenatom oder eine Nitrogruppe bedeuten.Process for the preparation of thiophosphonic acid esters The invention relates to a process for the preparation of thiophosphonic acid esters of the general formula in which Ri and R2 are low molecular weight alkyl radicals, X and X2 are oxygen: or sulfur atoms and Y is hydrogen or halogen or a nitro group.
Aus den bekanntgemachten Unterlagen des österreichischen Patents 213 905 sind bereits Dialkyl,-thiol- bzw. -thionothiolphosphorsäureester von N-Methylolbenzoxazolonen bekannt. Die vorgenannten Verbindungen zeichnen sich durch eine insektizide und akarizide Wirkung sowie eine fungitoxische Wirksamkeit bei guter Pflanzenverträglichkeit aus.From the published documents of the Austrian patent 213 905 are already dialkyl, thiol or thionothiol phosphoric acid esters of N-methylolbenzoxazolones known. The aforementioned compounds are characterized by an insecticidal and acaricidal effect and fungitoxic effectiveness with good plant tolerance the end.
Weiterhin werden in der deutschen Patentschrift 1064 064 Thionophosphorsäureester heterocyclischer N-Methylol-Verbindungen, die eine gute kontaktinsektizide Wirkung besonders gegenüber Blattläusen, Spinnmilben, Mückenlarven und Kornkäfern besitzen, beschrieben.Furthermore, in the German patent 1064 064 thionophosphoric acid esters heterocyclic N-methylol compounds that have a good contact insecticidal effect especially against aphids, spider mites, mosquito larvae and grain weevils, described.
Es wurde nun gefunden, daß Thiophosphonsäureester der oben angegebenen Konstitution glatt und mit guten Ausbeuten erhalten werden, wenn man N-Halogen-methyl-Verbindungen der allgemeinen Formel mit dem Salz eines Thiophosphonsäureesters der allgemeinen Formel in an sich bekannter Weise umsetzt, wobei in letztgenannten Formeln die Symbole Ri, R2, Xi, X2 und Y die weiter oben angegebene Bedeutung besitzen.It has now been found that thiophosphonic acid esters of the above constitution are obtained smoothly and in good yields if N-halomethyl compounds of the general formula are used with the salt of a thiophosphonic acid ester of the general formula implemented in a manner known per se, the symbols Ri, R2, Xi, X2 and Y in the last-mentioned formulas having the meaning given above.
Die erfindungsgemäße Umsetzung wird zweck- ; mäßig bei Zimmer- oder schwach erhöhter Temperatur sowie in Gegenwart eines inerten, organischen Lösungsmittels vorgenommen. Für den genannten Zweck kommen unter anderem niedrigsiedende Ketone, wie Aceton oder Methyl-äthyl-keton, niedere Alkohole (Methanol, Äthanol, Propanol), ferner Acetonitril oder Dioxan' in Frage, aber auch Lösungsmitteigemische, z. B. Wasser-Alkohol oderAceton-Wasser, sind verwendbar.The implementation according to the invention is expedient; moderate for room or slightly elevated temperature and in the presence of an inert, organic solvent performed. Low-boiling ketones, among others, are used for the stated purpose, such as acetone or methyl ethyl ketone, lower alcohols (methanol, ethanol, propanol), also acetonitrile or dioxane 'in question, but also solvent mixtures, eg. B. Water-alcohol or acetone-water are usable.
Im allgemeinen werden die beiden Reaktionskomponenten in etwa äquimolaren Mengen zur Reaktion gebracht, doch ist es in einigen Fällen vorteilhaft, das thiol- bzw. thionothiolphosphonsaure Salz in geringem Uberschuß anzuwenden.In general, the two reaction components are approximately equimolar Quantities reacted, but in some cases it is advantageous to use the thiol- or use thionothiolphosphonic acid salt in a slight excess.
Die als Ausgangsmaterial für das erfindungsgemäße Verfahren benötigten N-Halogen-methyl-Derivate des Benzoxazolons oder Benzthiazolons können in bekannter Weise aus den entsprechenden N-Methylol-Verbindungen durch Umsetzung mit Thionylchlorid oder konzentrierter Salzsäure hergestellt werden.The required as starting material for the process according to the invention N-halomethyl derivatives of benzoxazolone or benzthiazolone can be used in known Way from the corresponding N-methylol compounds by reaction with thionyl chloride or concentrated hydrochloric acid.
Die erfindungsgemäß herstellbaren Thiol- bzw. Dithiophosphonsäureester stellen zum Teil kristalline Substanzen dar, die sich durch Umkristallisieren aus geeigneten Lösungsmitteln leicht reinigen lassen. Teilweise handelt es sich bei den Verfahrensprodukten um viskose Öle, die auch im Hochvakuum nicht ohne Zersetzung destillierbar sind.The thiol or dithiophosphonic acid esters which can be prepared according to the invention are partly crystalline substances that result from recrystallization Can be easily cleaned using suitable solvents. In some cases it is the process products are viscous oils that do not decompose even in a high vacuum are distillable.
Die Verfahrensprodukte zeichnen sich durch hervorragende insektizide Wirksamkeit aus. Sie sollen deshalb als Schädlingsbekämpfungsmittel, vor allem im Pflanzenschutz Verwendung finden.The products of the process are characterized by excellent insecticides Effectiveness. They should therefore be used as pesticides, especially in Find plant protection use.
Gegenüber den aus den bekanntgemachten Unterlagen des österreichischen
Patents 213 905 sowie aus der deutschen Patentschrift 1064 064 bekannten
Verbindungen analoger Konstitution und gleicher
Wirkungsrichtung
zeichnen sich . die Verfahrensprodukte bei ihrer Anwendung gegen eine große Anzahl
von Schadinsekten durch überraschende, technisch wertvolle Eigenschaften aus. Diese
eindeutige Uberlegenheit - der verfahrensgemäß herstellbaren Thiophosphonsäureester
geht aus den im folgenden tabellarisch zusammengestellten Ergebnissen von Vergleichsversuchen
hervor:
Analyse: C12H1603NS2P (Molgewicht 317,4) Berechnet ... N 4,3 1, S 20,20, P 9,76; gefunden . . . N 4,35, S 20,58, P 10,03.Analysis: C12H1603NS2P (molecular weight 317.4) Calculated ... N 4.3 1, S 20.20, P 9.76; found . . . N 4.35, S 20.58, P 10.03.
Die Verbindung zeigt an der Ratte per os eine mittlere Toxizität (DL5o) von 25 mg je Kilogramm Tier. Beispiel 2 87 g (0,55 Mol) des Ammoniumsalzes des Methylthiolphosphonsäureäthylesters und 99 g (0,43 Mol) N-Brommethylbenzoxazolon-(2) (Fp.158°C) werden in 200 ccm Acetonitril suspendiert, wobei eine schwach exotherme Reaktion eintritt. Die Temperatur der Mischung wird durch Kühlung auf 40°C gehalten. Man rührt das Reaktionsgemisch über Nacht bei Zimmertemperatur, gießt es dann in Wasser und nimmt das abgeschiedene Dl in Benzol auf. Die benzolische Lösung wird zunächst mit Wasser, dann mit Natriumbicarbonatlösung und schließlich nochmals mit Wasser gewaschen. Nach dem Trocknen der Benzollösung über Natriumsulfat und Abdestillieren des Lösungsmittels hinterbleiben 100 g (80,5% der Theorie) des Esters in Form eines grünlichen, dickflüssigen Ules.The compound shows a mean toxicity (DL50) of 25 mg per kilogram of animal in the rat per os. Example 2 87 g (0.55 mol) of the ammonium salt of methylthiolphosphonic acid ethyl ester and 99 g (0.43 mol) of N-bromomethylbenzoxazolone- (2) (melting point 158 ° C.) are suspended in 200 cc of acetonitrile, a slightly exothermic reaction occurring. The temperature of the mixture is kept at 40 ° C. by cooling. The reaction mixture is stirred overnight at room temperature, then poured into water and the Dl which has separated out is taken up in benzene. The benzene solution is washed first with water, then with sodium bicarbonate solution and finally again with water. After the benzene solution has been dried over sodium sulfate and the solvent has been distilled off, 100 g (80.5% of theory) of the ester remain in the form of a greenish, viscous ole.
Analyse: C11H1404NSP (Molgewicht 287,3) Berechnet ... N 4,89, S 11,17, P 10,78; gefunden ... N 4,82, S 11,78, P 10,38.Analysis: C11H1404NSP (molecular weight 287.3) Calculated ... N 4.89, S 11.17, P 10.78; found ... N 4.82, S 11.78, P 10.38.
Die mittlere Giftigkeit der Verbindung beträgt an der Ratte per os 5 mg je Kilogramm Tier. Man rührt eine Suspension von 50 g (0,22 Mol) N-Brommethylbenzoxazolon-(2) (Fp. 158°C) und 58 g (0,26 Mol) des Kaliumsalzes des Isopropylthionothiolphosphonsäureäthyiesters in 200 ccm Acetonitril 1/2 Stunde, wobei die Innentemperatur der Mischung allmählich auf 32 bis 33°C ansteigt. Zur Vervollständigung der Umsetzung wird das Reaktionsgemisch anschließend noch 1/2 Stunde auf 50°C erwärmt. Nach dem Erkalten gießt man es in Wasser, impft das unter Umständen zunächst ölig anfallende Reaktionsprodukt gegebenenfalls an und saugt es ab. Aus Methanol umkristallisiert erhält man den Ester in Form farbloser Nädelchen vom Schmelzpunkt 62°C. Ausbeute 70 g, d. h. 96% der Theorie.The mean toxicity of the compound in rats is 5 mg per os per kilogram of animal. A suspension of 50 g (0.22 mol) of N-bromomethylbenzoxazolone- (2) (melting point 158 ° C.) and 58 g (0.26 mol) of the potassium salt of isopropylthionothiolphosphonic acid ether in 200 cc of acetonitrile is stirred for 1/2 hour the internal temperature of the mixture gradually rises to 32 to 33 ° C. To complete the reaction, the reaction mixture is then heated to 50 ° C. for a further 1/2 hour. After cooling, it is poured into water, the reaction product, which may initially be oily, is inoculated, if necessary, and it is filtered off with suction. Recrystallized from methanol, the ester is obtained in the form of colorless needles with a melting point of 62.degree. Yield 70 g, ie 96% of theory.
Analyse: C13H1sO:3NS2P (Molgewicht 331,4) Berechnet ... N 4,14, S 19,41, P 9,38; gefunden ... N 4,27, S 19,45, P 9,51. Man suspendiert 49 g (0,2 Mol) N-Brommethylbenzthiazolon-(2) und 46 g (0,2 Mol) des Kaliumsalzes des Äthylthionothiolphosphonsäureäthylesters in 200 ccm Acetonitril und rührt die Suspension über Nacht bei Zimmertemperatur. Auf Zugabe von 300 ccm Wasser zum Reaktionsgemisch fällt ein Dl aus. Letzteres wird in Benzol aufgenommen und die benzolische Lösung in der in den vorstehenden Beispielen beschriebenen Weise aufgearbeitet. Nach Abdestillieren des Lösungsmittels erhält man ein hellgelbes 01, das beim Anreiben mit Isopropylalkohol kristallin erstarrt. Fp. 48'C. Ausbeute 46 g, d. h. 69,7% der Theorie. 15,6 g (0,1 Mol) Methylthionothiolphosphonsäureäthylester werden mit einer Natriumäthylatlösung, die 0,1 Mol Natrium gelöst enthält, neutralisiert. Darauf wird die Mischung kurze Zeit nachgerührt und dann mit 19,95 g (0,1 Mol) N-Chlormethylbenzthiazolon-(2) versetzt, wobei die Innentemperatur von selbst auf etwa 35°C ansteigt. Zur Vervollständigung der Umsetzung erhitzt man das Reaktionsgemisch noch 3 Stunden auf 40 bis 50°C und kühlt es anschließend auf Raumtemperatur ab. Danach :wird das ausgeschiedene Natriumchlorid abgesaugt, das Filtrat im Vakuum eingeengt und der Rückstand in Benzol aufgenommen. Die benzolische Lösung wäscht man mit Wasser, trocknet sie mit Natriumsulfat und destilliert das Benzol im Vakuum ab. Als Rückstand hinterbleiben 19,9 g (62,5% der Theorie) des Esters in Form eines braunen Ules. Blattläuse werden von 0,01%igen, Raupen von 0,1%igen zu 100% und Spinnmilben sogar noch von 0,001%igen Lösungen der Verbindung zu 95% abgetötet. In einer Konzentration von 0,1% wirkt der Ester auch gegen Spinnmilbeneier, während die systemische Wirkung einer 0,1%igen Lösung auf Blattläuse 50% beträgt. DL50 an der Ratte per os = 50 mg/kg. Wie im vorhergehenden Beispiel werden 18,35 g (0,1 Mol) N-Chlormethylbenzoxazolon-(2) mit 17,8 g (0,1 Mol) des Natriumsalzes des Methylthionothiolphosphonsäureäthylesters umgesetzt. Nach dem Aufarbeiten in der im Beispiel 10 beschriebenen Weise erhält man 18,8 g (62% der Theorie) des Esters als i hellbraunes ifl.Analysis: C13H1sO: 3NS2P (molecular weight 331.4) Calculated ... N 4.14, S 19.41, P 9.38; found ... N 4.27, S 19.45, P 9.51. 49 g (0.2 mol) of N-bromomethylbenzthiazolone (2) and 46 g (0.2 mol) of the potassium salt of ethylthionothiolphosphonic acid ethyl ester are suspended in 200 cc of acetonitrile and the suspension is stirred overnight at room temperature. When 300 cc of water are added to the reaction mixture, a DI precipitates out. The latter is taken up in benzene and the benzene solution is worked up in the manner described in the preceding examples. After distilling off the solvent, a light yellow 01, which solidifies on trituration with isopropyl alcohol crystalline. M.p. 48'C. Yield 46 g, ie 69.7% of theory. 15.6 g (0.1 mol) of methylthionothiolphosphonic acid ethyl ester are neutralized with a sodium ethylate solution containing 0.1 mol of sodium in solution. The mixture is then stirred for a short time and then 19.95 g (0.1 mol) of N-chloromethylbenzthiazolone- (2) are added, the internal temperature rising to about 35 ° C. by itself. To complete the reaction, the reaction mixture is heated to 40 to 50 ° C. for a further 3 hours and then cooled to room temperature. Then: the precipitated sodium chloride is filtered off with suction, the filtrate is concentrated in vacuo and the residue is taken up in benzene. The benzene solution is washed with water, dried with sodium sulfate and the benzene is distilled off in vacuo. The residue left behind was 19.9 g (62.5% of theory) of the ester in the form of a brown ole. Aphids are killed by 0.01%, caterpillars by 0.1% by 100% and spider mites even by 0.001% solutions of the compound to 95%. At a concentration of 0.1%, the ester is also effective against spider mite eggs, while the systemic effect of a 0.1% solution on aphids is 50%. DL50 in the rat orally = 50 mg / kg. As in the previous example, 18.35 g (0.1 mol) of N-chloromethylbenzoxazolone- (2) are reacted with 17.8 g (0.1 mol) of the sodium salt of methylthionothiolphosphonic acid ethyl ester. After working up in the manner described in Example 10, 18.8 g (62% of theory) of the ester are obtained as a light brown ifl.
0,001%ige Lösungen der Verbindung vernichten Blattläuse und Spinnmilben noch zu 98 bzw. 990%, während Raupen von 0,1%igen Lösungen 1000/öig abgetötet werden: -In einer Konzentration von s 0;1% ist der Ester .bei der Anwendung gegen Spinnmilben auch ovizid wirksam. DLso an der Ratte per os = 20 mg/kg.0.001% solutions of the compound destroy aphids and spider mites still to 98 or 990%, while caterpillars are killed by 0.1% solutions 1000 / oig: -In a concentration of s 0; 1%, the ester is used against spider mites also effective as an ovicidal agent. DLso on the rat orally = 20 mg / kg.
Claims (1)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF32583A DE1226584B (en) | 1960-09-22 | 1960-11-19 | Process for the preparation of thiophosphonic acid esters |
| CH1067361A CH409964A (en) | 1960-09-22 | 1961-09-14 | Process for the preparation of thio- or dithiophosphonic (on, in) acid esters |
| NL269468A NL138945B (en) | 1960-09-22 | 1961-09-21 | PROCESS FOR PREPARING ORGANIC PHOSPHORUS COMPOUNDS WITH INSECTICIDE ACTION. |
| DK375661A DK102940C (en) | 1960-09-22 | 1961-09-21 | Agent for controlling harmful organisms and a process for the preparation of thio- or dithiophosphoric (on-, in-) acid esters for use in the agent. |
| GB3409761A GB928147A (en) | 1960-09-22 | 1961-09-22 | Phosphorus-containing esters |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0032171 | 1960-09-22 | ||
| DEF32583A DE1226584B (en) | 1960-09-22 | 1960-11-19 | Process for the preparation of thiophosphonic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1226584B true DE1226584B (en) | 1966-10-13 |
Family
ID=25974778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF32583A Pending DE1226584B (en) | 1960-09-22 | 1960-11-19 | Process for the preparation of thiophosphonic acid esters |
Country Status (5)
| Country | Link |
|---|---|
| CH (1) | CH409964A (en) |
| DE (1) | DE1226584B (en) |
| DK (1) | DK102940C (en) |
| GB (1) | GB928147A (en) |
| NL (1) | NL138945B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT213905B (en) * | 1958-12-30 | 1961-03-10 | Albert Ag Chem Werke | Process for the preparation of new thiol or thionothiol phosphoric acid esters |
-
1960
- 1960-11-19 DE DEF32583A patent/DE1226584B/en active Pending
-
1961
- 1961-09-14 CH CH1067361A patent/CH409964A/en unknown
- 1961-09-21 DK DK375661A patent/DK102940C/en active
- 1961-09-21 NL NL269468A patent/NL138945B/en not_active IP Right Cessation
- 1961-09-22 GB GB3409761A patent/GB928147A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT213905B (en) * | 1958-12-30 | 1961-03-10 | Albert Ag Chem Werke | Process for the preparation of new thiol or thionothiol phosphoric acid esters |
Also Published As
| Publication number | Publication date |
|---|---|
| DK102940C (en) | 1965-10-25 |
| CH409964A (en) | 1966-03-15 |
| NL138945B (en) | 1973-05-15 |
| GB928147A (en) | 1963-06-06 |
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