DE1119849B - Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters - Google Patents
Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid estersInfo
- Publication number
- DE1119849B DE1119849B DEF28805A DEF0028805A DE1119849B DE 1119849 B DE1119849 B DE 1119849B DE F28805 A DEF28805 A DE F28805A DE F0028805 A DEF0028805 A DE F0028805A DE 1119849 B DE1119849 B DE 1119849B
- Authority
- DE
- Germany
- Prior art keywords
- allyl
- phosphoric acid
- thiol
- alkyl
- preparation
- 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
- 238000002360 preparation method Methods 0.000 title claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 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 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 241001124076 Aphididae Species 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 241001454295 Tetranychidae Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004606 Fillers/Extenders Substances 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
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- OXLDKMFHLBAHLV-UHFFFAOYSA-N bis(prop-2-enyl) hydrogen phosphite Chemical compound C=CCOP(O)OCC=C OXLDKMFHLBAHLV-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts 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
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
- C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von O-AIlyl-O-alkyl-thiol-phosphorsäureestern Es wurde gefunden, daß man O-Allyl-O-alkylthiol-phosphorsäureester dadurch herstellen kann, daß man O-allyl-O-alkyl-thiol-phosphorsaure Salze mit gegebenenfalls substituierten Alkylchloriden umsetzt. Process for the preparation of O-Allyl-O-alkyl-thiol-phosphoric acid esters It has been found that O-allyl-O-alkylthiol-phosphoric acid esters can be produced in this way can that one O-allyl-O-alkyl-thiol-phosphoric acid salts with optionally substituted Reacts alkyl chlorides.
Die als Ausgangsmaterialien benötigten O-allyl-O-alkyl-thiol-phosphorsauren Salze können auf bequeme Art und Weise dadurch hergestellt werden, daß man an Diallylphosphit in Gegenwart von Alkalialkoholaten Schwefel anlagert. Hierbei entsteht nicht, wie erwartet werden müßte, das entsprechende O, O-diallyl-thionophosphorsaure Alkalisalz, sondern unter Austausch einer Allylgruppe gegen den Alkoholrest des verwendetenNatriumalkoholates das entsprechende O-allyl-O-alkyl-thionophosphorsaure Alkalisalz, das sich in seiner tautomeren Thiolform alkylieren läßt zu den neuen erfindungsgemäßen Verbindungen. The O-allyl-O-alkyl-thiol-phosphoric acids required as starting materials Salts can be conveniently prepared by reacting on diallyl phosphite accumulates sulfur in the presence of alkali alcoholates. This does not arise how would have to be expected, the corresponding O, O-diallyl-thionophosphoric acid alkali salt, but by exchanging an allyl group for the alcohol residue of the sodium alcoholate used the corresponding O-allyl-O-alkyl-thionophosphoric acid alkali salt, which is in his tautomeric thiol form can be alkylated to give the new compounds according to the invention.
Am Beispiel der Umsetzung des O, O-Diallylphosphits mit Schwefel und Natrium-methylat sowie der weiteren erfindungsgemäßen Reaktion des entstandenen O-allyl-O-methylthiol-phosphorsauren Na- triums mit einem gegebenenfalls substituierten Alkylhalogenid sei das Verfahren erläutert : In vorstehenden Gleichungen bedeutet R einen gegebenenfalls substituierten Alkylrest und X ein Halogenatom.The process is explained using the example of the reaction of O, O-diallyl phosphite with sulfur and sodium methylate and the further inventive reaction of the sodium O-allyl-O-methylthiol-phosphoric acid with an optionally substituted alkyl halide: In the above equations, R denotes an optionally substituted alkyl radical and X denotes a halogen atom.
Die erfindungsgemäß erhältlichen neuen Verbindungen stellen Schädlingsbekämpfungsmittel dar, die vor allem als Insektizide Verwendung finden sollen. The new compounds obtainable according to the invention represent pesticides which are to be used primarily as insecticides.
Ihre Anwendung geschieht auf prinzipiell bekannte Art und Weise, d. h. in Verbindung mit geeigneten festen oder flussigen Streck-oder Verdünnungsmitteln.They are used in a manner known in principle, i. H. in conjunction with suitable solid or liquid extenders or thinners.
Die gemäß Erfindung herstellbaren O-Allyl-O-alkylthiol-phosphorsäure-S-alkylester
sind, wie aus den nachfolgenden Vergleichsversuchen eindeutig hervorgeht, den bekannten,
analog gebauten O, O-Dialkylthiol-phosphorsäure-S-alkylestern hinsichtlich ihrer
insektiziden Wirksamkeit deutlich überlegen. Es wurden verglichen : Der verfahrensgemäß
herstellbare O-Allyl-O-methyl-thiol-phosphorsäure-S- (4-chlor-
phenyl)-methylester
der Formel
mit dem bekannten O, O-Dimethyl-thiol-phosphorsäure-S-(4-chlorphenyl)-methylester
der Formel
Die Ergebnisse der Vergleichsversuche sind in der folgenden Tabelle zusammengefaßt.
Beispiel 1 48 g O-allyl-O-methyl-thiol-phosphorsaures Natrium (0, 25 Mol) werden in 100 ccm Acetonitril gelöst. Dazu gibt man unter Rühren 40 g (0, 25 Mol) a-Chlormethylthiophenyläther. Man erwärmt 1 Stunde auf 50°C und gibt dann das Reaktionsprodukt in 300 ccm Eiswasser. Das ausgeschiedene 01 wird in 300 ccm Benzol aufgenommen, mit Wasser neutral gewaschen und anschließend mit Natriumsulfat getrocknet. Nach dem Abdestillieren des Losungsmittels erhält man 54 g des neuen Esters als wasserunlösliches, gelbes Öl. Ausbeute : 68 °/0 der Theorie.example 1 48 g of O-allyl-O-methyl-thiol-phosphoric acid sodium (0.25 mol) are dissolved in 100 cc of acetonitrile. 40 g (0.25 mol) of α-chloromethylthiophenyl ether are added with stirring. The mixture is heated to 50 ° C. for 1 hour and then the reaction product is poured into 300 cc of ice water. The precipitated oil is taken up in 300 cc of benzene, washed neutral with water and then dried with sodium sulfate. After the solvent has been distilled off, 54 g of the new ester are obtained as a water-insoluble, yellow oil. Yield: 68% of theory.
Berechnet für Mol 290... S 20, 2 °/0, P 9, 8 °/o ; gefunden.............. S 21,0%, P 10, 2%. Calculated for moles 290 ... S 20.2 ° / 0, P 9.8%; found.............. S 21.0%, P 10.2%.
Blattläuse werden noch in einer Konzentration von 0, 01% 100%ig abgetötet. DL50 Ratte per os : 5 mg/kg. Aphids are killed at a concentration of 0.01% 100%. DL50 rat orally: 5 mg / kg.
Beispiel 2 48 g (0, 25 Mol) O-allyl-O-methyl-thiol-phosphorsaures Natrium werden in 100 ccm Acetonitril gelöst.Example 2 48 g (0.25 mol) of O-allyl-O-methyl-thiol-phosphoric acid sodium are dissolved in 100 cc of acetonitrile.
Anschließend gibt man bei 75°C 35 g (0, 25 Mol) ß-[Diäthylamino]-äthylchlorid hinzu, Man hält noch 1 Stunde bei 75°C und arbeitet dann in üblicher Weise auf. Es werden 35 g des neuen Esters als wasserlösliches, schwachgelbes Ö1 erhalten. Ausbeute : 48% der Theorie.Then at 75 ° C. 35 g (0.25 mol) of β- [diethylamino] ethyl chloride are added added, it is kept at 75 ° C. for 1 hour and then worked up in the usual way. 35 g of the new ester are obtained as a water-soluble, pale yellow oil. Yield: 48% of theory.
Berechnet für Mol 267... N 7,8%, S 10,9%, P 10,7%; gefunden .............. N 6,8%, S 11,0%, P 11,0%. Calculated for Mol 267 ... N 7.8%, S 10.9%, P 10.7%; found .............. N 6.8%, S 11.0%, P 11.0%.
Beispiel 3 48 g (0, 25 Mol) O-allyl-O-methyl-thiol-phosphorsaures Natrium werden in 100 ccm Acetonitril gelöst.Example 3 48 g (0.25 mol) of O-allyl-O-methyl-thiol-phosphoric acid sodium are dissolved in 100 cc of acetonitrile.
Bei 40°C gibt man unter Rühren 49 g a-Chlormethyl-(4-chlor-phenyl)-thioäther (0, 25 Mol) hinzu. Man läßt 1 Stunde bei 50° C rühren und arbeitet dann in üblicher Weise auf. Es werden 50 g des neuen Esters als wasserunlösliches, schwachgelbes 01 erhalten. Ausbeute : 59"/odeur Theorie.At 40 ° C., 49 g of α-chloromethyl (4-chlorophenyl) thioether are added with stirring (0.25 moles). The mixture is stirred for 1 hour at 50.degree. C. and then carried out in a conventional manner Way up. There are 50 g of the new ester as a water-insoluble, pale yellow 01 received. Yield: 59 "/ or theory.
Berechnet für Mol 325... S 18, 2°/os P 9, 4°/0, Cl 12, 10/0 ; gefunden .............. S 19,2%, P 9,6%, Cl 1 1, 8 °/0. Calculated for moles 325 ... S 18.2 ° / os P 9.4 ° / 0, Cl 12, 10/0; found .............. S 19.2%, P 9.6%, Cl 1 1.8 ° / 0.
DL50 Ratte per os : 25 mg/kg. Blattläuse werden in einer Konzentration von 0, 001 °/o noch 100°/oig abgetötet. DL50 rat orally: 25 mg / kg. Aphids are in a concentration of 0.001% still 100% killed.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF28805A DE1119849B (en) | 1959-06-27 | 1959-06-27 | Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF28805A DE1119849B (en) | 1959-06-27 | 1959-06-27 | Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1119849B true DE1119849B (en) | 1961-12-21 |
Family
ID=7093032
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF28805A Pending DE1119849B (en) | 1959-06-27 | 1959-06-27 | Process for the preparation of O-allyl-O-alkyl-thiol-phosphoric acid esters |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1119849B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB785030A (en) * | 1954-07-12 | 1957-10-23 | Fisons Pest Control Ltd | Process for the production of sulphinyl ethyl thiophosphates |
DE1056117B (en) * | 1957-01-05 | 1959-04-30 | Bayer Ag | Process for the preparation of O, O-dialkylthiolphosphoric acid and -thiolthionophosphoric acid-S-gamma-cyanallyl esters |
-
1959
- 1959-06-27 DE DEF28805A patent/DE1119849B/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB785030A (en) * | 1954-07-12 | 1957-10-23 | Fisons Pest Control Ltd | Process for the production of sulphinyl ethyl thiophosphates |
DE1056117B (en) * | 1957-01-05 | 1959-04-30 | Bayer Ag | Process for the preparation of O, O-dialkylthiolphosphoric acid and -thiolthionophosphoric acid-S-gamma-cyanallyl esters |
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