DE1058046B - Process for the preparation of O, O-dialkylthionophosphoric acid-O-dichlorovinyl esters - Google Patents
Process for the preparation of O, O-dialkylthionophosphoric acid-O-dichlorovinyl estersInfo
- Publication number
- DE1058046B DE1058046B DEF20461A DEF0020461A DE1058046B DE 1058046 B DE1058046 B DE 1058046B DE F20461 A DEF20461 A DE F20461A DE F0020461 A DEF0020461 A DE F0020461A DE 1058046 B DE1058046 B DE 1058046B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- dichlorovinyl
- esters
- preparation
- chloral
- 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 7
- 150000002148 esters Chemical class 0.000 title claims description 6
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- AWOYKRJEPKDQRB-UHFFFAOYSA-N 2,2-dichloroethenoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical class OP(O)(=S)OC=C(Cl)Cl AWOYKRJEPKDQRB-UHFFFAOYSA-N 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- NVOBROMNCLKBMK-UHFFFAOYSA-N trichloro(diethyl)-$l^{5}-phosphane Chemical compound CCP(Cl)(Cl)(Cl)CC NVOBROMNCLKBMK-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
- C07F9/173—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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Es ist bekannt, daß man durch Umsetzung von Trialkylphosphiten mit Chloral ohne äußere Wärmezufuhr O.O-Dialkyl-phosphorsäure-O-dichlorvinylester herstellen kann (vgl. deutsche Patentanmeldung N 3376 IVb/12o).It is known that by reacting trialkyl phosphites produce O.O-dialkyl-phosphoric acid-O-dichlorovinyl ester with chloral without external heat supply can (see German patent application N 3376 IVb / 12o).
Es wurde nun gefunden, daß man 0,0-Dialkylthionophosphorsäure-O-dichlorvinylestcr der FormelIt has now been found that 0,0-dialkylthionophosphoric acid-O-dichlorovinylestcr the formula
Alkyl — Ο—1Q-0 — CH = CCl2
Alkyl— Ο— Γ =SAlkyl - Ο— 1 Q-0 - CH = CCl 2
Alkyl— Ο— Γ = S
erhält, wenn man 0,0-Dialkylpliosphongsäure-S-aikylestcr mit Chloral bei erhöhter Temperatur umsetzt.obtained when 0,0-dialkylpliosphongic acid-S-aikylestcr Reacts with chloral at elevated temperature.
Die für das~erfindungsgemäße Verfahren verwendeten leicht oxydablen 0,0-Dialkylphosphorigsäure-S-alkylester können nach bekannten Methoden hergestellt werden, z. B. indem man Alkyhnercaptane mit Dialkylphosphorigsäurechloriden umsetzt. (Vgl. Arbusow, Nikonorow: Doklady Akad. Nauk S. S. S. R., 62, 75 [1948] = Chcm. Abstracts, Bd. 43 [1949], Sp. 1004c.) Bei einer bevorzugten Ausführungsform des neuen Verfahrens isoliert man die gebildeten 0,0-Dialkylphosphorigsäure-S-alkylester nicht, sondern setzt das so erhaltene Reaktionsprodukt mit dem Chloral um.The ones used for the method according to the invention easily oxidizable 0,0-dialkylphosphorous acid-S-alkyl ester can be prepared by known methods, e.g. B. by using Alkyhnercaptans with Dialkylphosphorigsäurechloriden implements. (Cf. Arbusow, Nikonorow: Doklady Akad. Nauk S. S. S. R., 62, 75 [1948] = Chcm. Abstracts, Vol. 43 [1949], Col. 1004c.) In a preferred embodiment of the new method, the formed 0,0-dialkylphosphorous acid S-alkyl ester not, rather, the reaction product thus obtained reacts with the chloral.
Diese Umsetzung wird zweckmäßigerweise in einem inerten organischen Lösungsmittel, wie z. B. Benzol, Toluol oder Chlorbenzol, vorgenommen. Temperaturen im Bereich von 60 und 800C haben sich bei der Durchführung des erfmdungsgemäßen Verfahrens besonders bewährt.This reaction is expediently carried out in an inert organic solvent, such as. B. benzene, toluene or chlorobenzene made. Temperatures in the range of 60 to 80 0 C have proven themselves in the implementation of the inventive method particularly.
Die neuen Dichlorvinylthionophosphorsäureestcr zeichnen sich — bei mäßiger Toxizität gegen Warmblüter — durch gute kontaktinsektizidc und vor allem eine systemische Wirkung aus, die den entsprechenden sauerstoffanalogen Verbindungen, welche in den bekanntgemachten Unterlagen der deutschen Patentanmeldung N 3376 IVb/12o beschrieben sind, nicht zukommt.The new dichlorovinylthionophosphoric acid esters stand out - with moderate toxicity to warm-blooded animals - by good contact insecticidec and above all a systemic effect that the corresponding oxygen-analogous compounds, which in the published documents of the German patent application N 3376 IVb / 12o is not applicable.
19 g Ο,Ο-Diäthylphosphorigsäure-Sjithylester (Kp.,: 45 bis 46° C) werden in 20 ecm BenzoT gelöst. Dazu werden unter Einleiten von Stickstoff und dauerndem Rühren bei 400C 15 g Chloral gegeben. Die Temperatur steigt von selbst auf 65° C. Man hält das Reaktionsprodukt noch 1 Stunde bei 7O0C und fraktioniert es dann. Es werden 18 g des O.O-Diäthyl-thionophosphorsäurc-O-dichlorvinylesters vom Kp^: 87 bis 880C als klares, wasserunlösliches Öl erhalten.19 g of Ο, Ο-diethylphosphorous acid sjithylester (bp.,: 45 to 46 ° C) are dissolved in 20 ecm BenzoT. To this end, 15 g of chloral are added while introducing nitrogen and continuously stirring at 40 ° C. The temperature rises by itself at 65 ° C. is maintained, the reaction product for 1 hour at 7O 0 C and then fractionated it. There are 18 g of OO-diethyl-O-thionophosphorsäurc dichlorvinylesters from Kp ^ receive 87-88 0 C as a clear, water-insoluble oil.
Analyse (für Molgewicht 265):Analysis (for molecular weight 265):
Berechnet S 12,6%, P 12,1 %, Cl 26,8%;Calculated S 12.6%, P 12.1%, Cl 26.8%;
gefunden S 11,8%, P 12,0 %, Cl 27,5%.found S 11.8%, P 12.0%, Cl 27.5%.
An der Ratte per os zeigt die neue Verbindung eine DL95 von 25 bis 30 mg/kg. Die vorliegende Verbindung wirkt gegenIn the rat per os, the new compound shows a DL 95 of 25 to 30 mg / kg. The present connection counteracts
Verfahren zur HerstellungMethod of manufacture
von Ο,Ο-Dialkylthionophosphorsäure-of Ο, Ο-dialkylthionophosphoric acid
O-dichlorvinylesternO-dichlorovinyl esters
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-BayerwerkPaint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk
Dr. Gerhard Sdirader, Wuppertal-Cronenberg, ist als Erfinder genannt wordenDr. Gerhard Sdirader, Wuppertal-Cronenberg, has been named as the inventor
Fliegen 0,0001% 75 %,Flying 0.0001% 75%,
Mückenlarven ... 0,0001 % 100%,Mosquito larvae ... 0.0001% 100%,
Blattläuse 0,01 % 100%,Aphids 0.01% 100%,
Spinnmilben 0,01 % 100%.Spider mites 0.01% 100%.
In 400 ecm Benzol werden unter dauerndem Einleiten von Stickstoff 32 g Äthylmercaptan und 42 g Pyridin gelöst. Dazu tropft man~unter Rühren 80 g Diäthylphosphorigsäurechlorid (Kp.12: 39 bis 4O0C), die in 100 ecm Benzol gelöst sind. Man hält die Reaktionstemperatur von 40° C 1 Stunde und gibt dann bei 700C 75 g Chloral zu. Man erwärmt dann noch x\t Stunde auf 8O0C, Kühlt auf Zimmertemperatur ab und gibt das Reaktionsprodukt in 500 ecm Eiswasser, dem 20 ecm 20%iger Salzsäure zugefügt waren. Nach dem Durchschütteln wird die benzolischc Lösung abgetrennt, mit Natriumsulfat getrocknet und fraktioniert. Es werden 97 g des O.O-Diäthyl-thionophosphorsäure-O-dichlorvinylesters vom Kp.,: 87° C erhalten.32 g of ethyl mercaptan and 42 g of pyridine are dissolved in 400 ecm of benzene while continuously passing in nitrogen. Thereto is added dropwise with stirring 80 g ~ Diäthylphosphorigsäurechlorid (Kp. 12: 39 to 4O 0 C) dissolved in 100 cc of benzene. The reaction temperature of 40 ° C is maintained 1 hour and then at 70 0 C 75 g chloral to. It is then heated for x \ t hour at 8O 0 C, cooled to room temperature, and are the reaction product in 500 cc of ice water, which were 20 cc of 20% hydrochloric acid added. After shaking, the benzene solution is separated off, dried with sodium sulfate and fractionated. 97 g of O-O-diethyl-thionophosphoric acid-O-dichlorovinyl ester with a boiling point of: 87 ° C. are obtained.
Analyse (für Molgewicht 265):Analysis (for molecular weight 265):
Berechnet S 12,6%, P 12,1^X126,8%;Calculated S 12.6%, P 12.1 ^ X 126.8%;
gefunden S 11,6%, P IW%% _GM8,1 %.S found 11.6%, P IW%%% _GM8,1.
Beispiel 3 4"** $ Example 3 4 "** $
46 g n-Butylmercaptan werden zusanmftBPmit 42 g Pyridin in 100 ecm Benzol gelöst. Unter Durchleiten von Stickstoff tropft man nun bei 00C 80 g Diäthylphosphorigsäurechlorid (gelöst in 100 ecm Benzol) zu. Man hält das Reaktionsprodukt 1 Stunde bei 100C und gibt dann bei 400C 75 g Chloral zu. Unter dauerndem Weiterrühren (die Innentempetatur steigt auf 650C) vollzieht sich die Umsetzung. Man hält das Reaktionsprodukt noch 1 Stunde bei 800C und arbeitet dann, wie im Beispiel 246 g of n-butyl mercaptan are dissolved together with 42 g of pyridine in 100 ecm of benzene. While passing nitrogen, then added dropwise at 0 0 C 80 g Diäthylphosphorigsäurechlorid (dissolved in 100 cc of benzene) was added. The reaction product is kept at 10 ° C. for 1 hour and then 75 g of chloral are added at 40 ° C. The reaction takes place with continued stirring (the internal temperature rises to 65 ° C.). The reaction product is kept at 80 ° C. for a further hour and then worked as in Example 2
90» 528/42290 »528/422
beschrieben, auf. Es werden 65 g des O.O-Diäthyl-thionophosphorsäure-O-dichlorvinylesters vom Kp.x: 85 bis 870C erhalten.described on. There are 65 g of OO-diethyl-O-thionophosphorsäure dichlorvinylesters from Kp x. Obtained 85 to 87 0 C.
Analyse (für Molgewicht 265):Analysis (for molecular weight 265):
Berechnet S 12,60Z0, Cl 26,8%;Calculated S 12.6 0 Z 0 , Cl 26.8%;
gefunden S 11,1 %, Cl 27,6 °/0.found S 11.1%, Cl 27.6 ° / 0 .
42 g Isopropylmercaptan werden zusammen mit 42 g Pyridin in 400 ecm Benzol gelöst. Unter dauerndem Durchleiten von Stickstoff gibt man zu dem Reaktionsprodukt bei O0C 80 g Diäthylphosphorigsäurechlorid (gelöst in 60 ecm Benzol). Man hält noch 1 Stunde bei 00C und gibt dann bei 400C 75 g Chloral zu. Die Temperatur steigt auf 750C. Man hält diese Temperatur noch V2 Stunde und arbeitet dann, wie im Beispiel 2 beschrieben, auf. Es werden 70 g des 0,0-Diäthyl-thionophosphorsäure-O-dichlorvinylesters vom Kp.,: 86 bis 87° C erhalten.42 g of isopropyl mercaptan are dissolved together with 42 g of pyridine in 400 ecm of benzene. While constantly passing nitrogen through, 80 g of diethylphosphorous acid chloride (dissolved in 60 ecm of benzene) are added to the reaction product at 0 ° C. It is held at 0 ° C. for a further 1 hour and then 75 g of chloral are added at 40 ° C. The temperature rises to 75 ° C. This temperature is maintained for a further V for 2 hours and then worked up as described in Example 2. 70 g of 0, 0-diethyl-thionophosphoric acid-O-dichlorovinyl ester with a boiling point of: 86 to 87 ° C. are obtained.
Analyse (für Molgewicht 265):Analysis (for molecular weight 265):
Berechnet S 12,6 °/o. P12,l°/0, C126,8°/0;Calculates S 12.6 per cent. P12, l ° / 0, C126,8 ° / 0;
gefunden S 11,5%, P 11,3%, Cl 27,9%.found S 11.5%, P 11.3%, Cl 27.9%.
14 g Äthyhnercaptan werden zusammen mit 17 g Pyridin in 100 ecm Benzol gelöst. Dazu gibt man im Stick14 g of Ethyhnercaptan are dissolved together with 17 g of pyridine in 100 ecm of benzene. For this you give in the stick
stoffstrom bei — 5° C 26 g Dimethylphosphorigsäurechlorid (Kp.6O: 350C). Dann tropft man bei + 100C 16 g Chloral zu. Die Temperatur steigt auf 520C. Man erwärmt noch 1J2 Stunde auf 7O0C und arbeitet dann in der üblichen Weise auf. Es werden 16 g des 0,0-Dimetbylthioiiophosphorsäure-O-dichlorvinylesters vom Kp.x: 70 bis 71°C erhalten.hydrogen at - 5 ° C 26 g Dimethylphosphorigsäurechlorid (b.p. 6O: 35 0 C.). Then 16 g of chloral are added dropwise at + 10 ° C. The temperature rises to 52 0 C. It is heated for 1 hour at J2 7O 0 C and then worked up in the usual manner. There are 16 g of 0,0-Dimetbylthioiiophosphorsäure-O-dichlorvinylesters from Kp x. Earn 70 ° to 71 ° C.
Analyse (für Molgewicht 237):Analysis (for molecular weight 237):
Berechnet S 13,4%, Cl 29,8%, P 12,8%;Calculated S 13.4%, Cl 29.8%, P 12.8%;
gefunden S 15,1 %, Cl27,1 %, P 11,7%.found S 15.1%, Cl27.1%, P 11.7%.
Claims (1)
Alkyl—-Ο— A =^SAlkyl - O - ΎΛ - O - CH = CCl 2
Alkyl —- Ο— A = ^ S
Deutsche Patentschrift Nr. 845 226;
deutsche Patentanmeldung N 3376 IVb (bekanntgemacht am 15. 5. 1952).Considered publications:
German Patent No. 845 226;
German patent application N 3376 IVb (published May 15, 1952).
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF20461A DE1058046B (en) | 1956-06-06 | 1956-06-06 | Process for the preparation of O, O-dialkylthionophosphoric acid-O-dichlorovinyl esters |
FR1179340D FR1179340A (en) | 1956-06-06 | 1957-05-24 | Dialcoyl-dichlorovinylthionophosphates and their production process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF20461A DE1058046B (en) | 1956-06-06 | 1956-06-06 | Process for the preparation of O, O-dialkylthionophosphoric acid-O-dichlorovinyl esters |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1058046B true DE1058046B (en) | 1959-05-27 |
Family
ID=7089689
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF20461A Pending DE1058046B (en) | 1956-06-06 | 1956-06-06 | Process for the preparation of O, O-dialkylthionophosphoric acid-O-dichlorovinyl esters |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE1058046B (en) |
FR (1) | FR1179340A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4127774A (en) * | 1977-06-20 | 1978-11-28 | Jerry Gillen | X-ray marker |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE845226C (en) * | 1948-05-10 | 1952-07-31 | Bataafsche Petroleum | lubricant |
-
1956
- 1956-06-06 DE DEF20461A patent/DE1058046B/en active Pending
-
1957
- 1957-05-24 FR FR1179340D patent/FR1179340A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE845226C (en) * | 1948-05-10 | 1952-07-31 | Bataafsche Petroleum | lubricant |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4127774A (en) * | 1977-06-20 | 1978-11-28 | Jerry Gillen | X-ray marker |
Also Published As
Publication number | Publication date |
---|---|
FR1179340A (en) | 1959-05-22 |
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