DE1074035B - Process for the preparation of thionoselenol phosphoric acid esters - Google Patents
Process for the preparation of thionoselenol phosphoric acid estersInfo
- Publication number
- DE1074035B DE1074035B DENDAT1074035D DE1074035DA DE1074035B DE 1074035 B DE1074035 B DE 1074035B DE NDAT1074035 D DENDAT1074035 D DE NDAT1074035D DE 1074035D A DE1074035D A DE 1074035DA DE 1074035 B DE1074035 B DE 1074035B
- Authority
- DE
- Germany
- Prior art keywords
- phosphoric acid
- acid esters
- thionoselenol
- preparation
- mol
- 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 6
- 150000003014 phosphoric acid esters Chemical class 0.000 title description 3
- 238000002360 preparation method Methods 0.000 title description 2
- -1 aryl selenium cyanides Chemical class 0.000 claims description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 241001465754 Metazoa Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MKRADGLBVYTOFR-UHFFFAOYSA-N (2-methoxyphenyl) selenocyanate Chemical compound COc1ccccc1[Se]C#N MKRADGLBVYTOFR-UHFFFAOYSA-N 0.000 description 1
- NMZVFVLLNNNSEC-UHFFFAOYSA-N (4-chlorophenyl)methyl selenocyanate Chemical compound Clc1ccc(C[Se]C#N)cc1 NMZVFVLLNNNSEC-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 241000500437 Plutella xylostella Species 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
- FSHJCRFWICDPNE-UHFFFAOYSA-N [4-(dimethylamino)phenyl] selenocyanate Chemical compound CN(C)C1=CC=C([Se]C#N)C=C1 FSHJCRFWICDPNE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DAMYNTNPMQUNBH-UHFFFAOYSA-N hexyl selenocyanate Chemical compound CCCCCC[Se]C#N DAMYNTNPMQUNBH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003958 selenols Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Verfahren zur Herstellung von Thionos elenolphosphorsäureestern In der deutschen Patentschrift 824046 ist ein Verfahren zur Herstellung von neutralen Estern der Selenolphosphorsäure beschrieben, welches dadurch gekennzeichnet ist, daß beliebig substituierte Alkyl-, Aralll-oder Arylselencyanide auf Dialkylphosphite oder deren Alkalisalze zur EinwiekurtgXgebracht werden. Process for the preparation of Thionos elenolphosphorsäureestern In the German patent specification 824046 is a process for the production of neutral Esters of selenol phosphoric acid described, which is characterized by that any substituted alkyl, aralli or aryl selenium cyanides on dialkyl phosphites or their alkali salts are brought to the EinwiekurtgX.
Die entsprechenden Thionoselenolphosphorsäureester sind aus der Literatur bisher noch nicht bekanntgeworden Es wurde gefunden, daß diese neuen Verbindungen dadurch herg-estellt werden können, daß man gegebenenfalls substftuierte Alkyl-, Aralkyl- oder Arylselencyanide- auf O,O-Dialkylthiolphosphite oder deren Alkalisalze zur Einwirkung bringt. Die Reaktion sei durch folgendes Formelschema erIädert: In den vorstehenden Formeln bedeutet X ein Wasserstoffatom oder Alkalimetallatom, R1 und R2 Alkylreste und R3 ein gegebenenfalls substituierter Alkyl-, Aralkyl-oder Arylrest.The corresponding thionoselenol phosphoric acid esters have not yet become known from the literature. It has been found that these new compounds can be produced by bringing optionally substituted alkyl, aralkyl or aryl selenium cyanides onto O, O-dialkylthiol phosphites or their alkali salts into action . The reaction is explained by the following equation: In the above formulas, X is a hydrogen atom or an alkali metal atom, R1 and R2 are alkyl radicals and R3 is an optionally substituted alkyl, aralkyl or aryl radical.
Die erfindungsgemäßen neuen Verbindungen sind hervorragende Schädlingsbekämpfungsmittel, die sich den Selenolphosphorsäureestern gegenüber durch erhöhte Wirksamkeit bei verringerter Toxizität gegen Warmblüter auszeichnen. Die neuen Verbindungen sollen im Pflanzenschutz Verwendung finden. Ihre Anwendung geschieht in prinzipiell bekannter Weise, d. h. bevorzugt in Verbindung mit geeigneten festen oder flüssigen Streck-oder Verdünnungsmitteln, gegebenenfalls unter Mitverwendung von Emulatoren, falls die Ester als solche nicht in eine echte Lösung zu bringen sind. The new compounds according to the invention are excellent pesticides, which compared to the selenol phosphoric acid esters through increased effectiveness characterized by reduced toxicity against warm-blooded animals. The new connections are supposed to are used in crop protection. Their application happens in principle well known Way, d. H. preferably in conjunction with suitable solid or liquid stretching or stretching Diluents, optionally with the use of emulators, if the Esters as such cannot be brought into a real solution.
Gegenüber den aus der deutschen Patentschrift 824046 bekannten Selenolphosphorsäureestern zeichnen sich die erfindungsgemäß erhältlichen Thionoselenolphosphorsäureester durch eine verbesserte Fliegen- und Raupenwirkung aus. Compared to the selenol phosphoric acid esters known from German patent 824046 The thionoselenol phosphoric acid esters obtainable according to the invention are distinguished by an improved fly and caterpillar effect.
Verglichen wurden der erfindungsgemäß erhältliche Ester der Formel (I) mit dem aus der vorgenannten deutschen Patentschrift bekannten Ester der Formel (II) Die Fliegenversuche wurden im sogenannten »Screen- ing«-Test durchgeführt, die Raupenversuche mit Raupen der species Plutella maculipennis auf Weißkohlblättern.The ester of the formula (I) obtainable according to the invention was compared with the ester of the formula (II) known from the aforementioned German patent The fly tests were carried out in the so-called “screening” test, the caterpillar tests with caterpillars of the species Plutella maculipennis on cabbage leaves.
Wie aus der nachfolgenden Tabelle außerdem ersichtlich ist, sind die erfindungsgemäß erhältlichen Verbindungen weniger toxisch als die aus der vorgenannten deutschen Patentschrift bekannten Selenolphosphorsäureester. As can also be seen from the table below, the compounds obtainable according to the invention are less toxic than those from the aforementioned German patent known selenol phosphoric acid ester.
I II Ratte per os: DL50 100 mg/kg DL50 10 mg/kg Fliegen . . . 0,1 % 100 01, 0,1 01o 100% 0,01 01o 100 01, 0,01 01o 001o Raupen . . 0,1 0/, 100% 0,l 01o 0°/0 Die folgenden Beispiele mögen das erfindungsgemäße Verfahren erläutern: Beispiel l 38 g (0,195 Mol) n-Hexylselencyanid (Kp.l 80°C) und 35 g (0,227 Mol) O,O-Diäthylthiolphosphit werden in 150 ccm Toluol gelöst und 3 Stunden im Ölbad unter Rückfluß erhitzt. Nach Erkalten wird destilliert. Dabei erhält man, nach einem geringen Vorlauf, den Ester als hellgelbes Ö1, das bei Kp.0,01 68O C siedet. Ausbeute 58 g, entsprechend 930/o der Theorie. Mittlere Toxizität Ratte per os: 100 mg/kg.I II rat per os: DL50 100 mg / kg DL50 10 mg / kg flies. . . 0.1% 100 01, 0.1 01o 100% 0.01 01o 100 01, 0.01 01o 001o caterpillars. . 0.1 0 /, 100% 0, l 01o 0 ° / 0 The following examples may explain the method according to the invention: Example 1 38 g (0.195 mol) of n-hexyl selenium cyanide (boiling point 80 ° C.) and 35 g (0.227 mol) of O, O-diethylthiol phosphite are dissolved in 150 cc of toluene and refluxed for 3 hours in an oil bath. After cooling, it is distilled. After a short forerun, the ester is obtained as a light yellow oil which boils at a boiling point of 0.01 68O C. Yield 58 g, corresponding to 930% of theory. Average toxicity rat orally: 100 mg / kg.
Beispiel 2 Zu einer Lösung von 57,5 g (0,25 Mol) p-Chlorbenzylselencyanid (F. 58 bis 590 C) und 46 g (0,3 Mol) O,O-Diäthylthiolphosphit in 150 ccm Benzol tropft man unter Wxühlen bei 10 bis 200 c Natriummethylatlösung, entsprechend 0,28 Mol Natrium. Nach halbstündigem Rühren wäscht man neutral, trocknet über Natriumsulfat und destilliert. Man erhält 82 g des Esters vom Kp.0,01 108° C als farbloses, wasserunlösliches Öl. Ausbeute 910/o der Theorie. Mittlere Toxizität Ratte per os: 100 mg/kg.Example 2 A solution of 57.5 g (0.25 mol) of p-chlorobenzyl selenium cyanide (m.p. 200 c of sodium methylate solution, corresponding to 0.28 mol of sodium. After stirring for half an hour, it is washed neutral, dried over sodium sulfate and distilled. 82 g of the ester with a boiling point of 0.01 108 ° C. are obtained as a colorless, water-insoluble oil. Yield 910 / o of theory. Average toxicity rat orally: 100 mg / kg.
Beispiel 3 53 g (0,25 Mol) 2-Methoxyphenylselencyanid und 46 g (0,3 Mol) O,O-Diäthylthiolphosphit werden in 150 ccm Benzol gelöst. Bei 200 C nicht übersteigender Temperatur tropft man unter Kühlen die 0,28 Mol Natrium entsprechende Menge Natriummethylat zu. Nach kurzem Nach- rühren bei Zimmertemperatur wäscht man neutral und verfährt wie in den vorstehenden Beispielen. Hellgelbes, viskoses Öl vom Kp.0,01 1060 C. Ausbeute 82 g, entsprechend 96,8 0/o der Theorie. Mittlere Toxizität Ratte per os: 250 mg/kg.Example 3 53 g (0.25 mol) of 2-methoxyphenyl selenium cyanide and 46 g (0.3 mol) of O, O-diethylthiol phosphite are dissolved in 150 cc of benzene. At a temperature not exceeding 200 ° C., the amount of sodium methylate corresponding to 0.28 mol of sodium is added dropwise with cooling. After stirring for a short time at room temperature, the product is washed neutral and the procedure is as in the preceding examples. Light yellow, viscous oil with a boiling point of 0.01 1060 C. Yield 82 g, corresponding to 96.8% of theory. Average toxicity rat orally: 250 mg / kg.
Beispiel 4 30 g (0,21 Mol) 4-Dimethylaminophenylselencyanid und 38,5 g (0,254 Mol) O,O-Diäthylthiolphosphit werden in 150 ccm Benzol 2 Stunden auf 60 bis 70" C erwärmt.Example 4 30 g (0.21 mol) of 4-dimethylaminophenyl selenium cyanide and 38.5 g (0.254 mol) of O, O-diethylthiol phosphite are heated to 60 to 70 ° C. in 150 cc of benzene for 2 hours.
Nach Erkalten verdünnt man mit Benzol, setzt etwas Tierkohle zu und filtriert. Durch Destillation erhält man den Ester rein als ein bei Kp.0,01 CL32° C siedendes, hellrotes Ö1. Ausbeute 60 g, entsprechend 81,6 0/o der Theorie Ratte per os DLg5 100 mg/kg.After cooling, you dilute with benzene, add some animal charcoal and filtered. By distillation, the ester is obtained in pure form at a boiling point of 0.01 CL32 ° C boiling, light red oil 1. Yield 60 g, corresponding to 81.6% of the theory rat per os DLg5 100 mg / kg.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1074035B true DE1074035B (en) | 1960-01-28 |
Family
ID=598186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1074035D Pending DE1074035B (en) | Process for the preparation of thionoselenol phosphoric acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1074035B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE824026C (en) * | 1950-12-03 | 1951-12-06 | Max Lindl | Device for engobing |
-
0
- DE DENDAT1074035D patent/DE1074035B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE824026C (en) * | 1950-12-03 | 1951-12-06 | Max Lindl | Device for engobing |
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