DE947368C - Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups - Google Patents

Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups

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Publication number
DE947368C
DE947368C DEF16085A DEF0016085A DE947368C DE 947368 C DE947368 C DE 947368C DE F16085 A DEF16085 A DE F16085A DE F0016085 A DEF0016085 A DE F0016085A DE 947368 C DE947368 C DE 947368C
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Germany
Prior art keywords
esters
phosphoric
preparation
acids containing
sulfoxide groups
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.)
Expired
Application number
DEF16085A
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German (de)
Inventor
Dr Walter Lorenz
Dr Rudolf Muehlmann
Dr Gerhard Schrader
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Bayer AG
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Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DEF21822A external-priority patent/DE1039511B/en
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF16085A priority Critical patent/DE947368C/en
Application granted granted Critical
Publication of DE947368C publication Critical patent/DE947368C/en
Expired legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
    • E04B2/02—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls built-up from layers of building elements
    • 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
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric 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
    • C07F9/1651—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
    • C07F9/28—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
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F3/00—Press section of machines for making continuous webs of paper
    • D21F3/02—Wet presses
    • D21F3/10—Suction rolls, e.g. couch rolls
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
    • E04B2/02—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls built-up from layers of building elements
    • E04B2002/0256—Special features of building elements
    • E04B2002/026—Splittable building elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

AUSGEGEBEN AM 16. AUGUST 1956ISSUED AUGUST 16, 1956

DEUTSCHES PATENTAMTGERMAN PATENT OFFICE

PATENTSCHRIFTPATENT LETTERING

KLASSE 12ο GRUPPE 2303 INTERNAT. KLASSE C 07cCLASS 12ο GROUP 2303 INTERNAT. CLASS C 07c

F 16085 IVb/12 οF 16085 IVb / 12 ο

Dr. Rudolf Mühlmann, Wuppertal-Elberfeld,Dr. Rudolf Mühlmann, Wuppertal-Elberfeld,

Dr. Walter Lorenz, Wuppertal-Elberfeld,Dr. Walter Lorenz, Wuppertal-Elberfeld,

und Dr. Gerhard Schrader, Opladenand Dr. Gerhard Schrader, Opladen

sind als Erfinder genannt wordenhave been named as inventors

Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-BayerwerkPaint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Verfahren zur Herstellung von Sulfoxydgruppen enthaltenden Estern der Phosphor- und ThiophosphorsäurenProcess for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups

Patentiert im Gebiet der Bundesrepublik Deutschland vom 7. November 1954 anPatented in the territory of the Federal Republic of Germany on November 7, 1954

Patentanmeldung bekanntgemacht am 23. Februar 1956Patent application published on February 23, 1956

Patenterteilung bekanntgemacht am 26. Juli 1956Patent issued July 26, 1956

Ester der Phosphor- und Thiophosphorsäuren bzw. der entsprechenden Phosphonsäuren, die in einer Estergruppe die Sulfoxydgruppe enthalten, sind bisher nicht beschrieben. Ebenfalls sind sulfoxydgruppenhaltige Alkohole, die zur Herstellung der genannten Ester dienen könnten, nicht beschrieben.Esters of phosphoric and thiophosphoric acids or the corresponding phosphonic acids, which are in a Ester groups containing sulfoxide groups have not yet been described. There are also sulfoxide groups Alcohols which could be used to produce the esters mentioned are not described.

Es wurde nun gefunden, daß sich Phosphorsäureester folgender allgemeiner FormelIt has now been found that phosphoric acid esters have the following general formula

O (S)O (S)

OR,OR,

R1 — S — R2 — X — P \R 1 - S - R 2 - X - P \

OR4 OR 4

in der R1 ein Alkyl-, Aralkyl- oder Arylrest, R2 ein organischer Rest ist, X = O oder S bedeutet oder eine direkte Bindung zwischen dem Rest R2 und dem Phosphoratom ist und R3 und R4 beliebige Alkylreste sind, zu den gewünschten Sulfoxyden mit konzentrierten Lösungen von Wasserstoffsuperoxyd oxydierbar sind.in which R 1 is an alkyl, aralkyl or aryl radical, R 2 is an organic radical, X = O or S or is a direct bond between the radical R 2 and the phosphorus atom and R 3 and R 4 are any alkyl radicals the desired sulfoxides can be oxidized with concentrated solutions of hydrogen peroxide.

Für die Herstellung der als Ausgangsmaterialien geeigneten Sulfidester sind verschiedene Verfahren bekannt. So kann man z. B. die Merkaptophosphonsäureester (in denen — X — entsprechend der vorstehend angegebenen allgemeinen Formel die direkte Bindung zwischen dem Rest R2 und dem Phosphoratom bedeutet) leicht durch Reaktion von Chloralkyl-Various processes are known for the preparation of the sulfide esters suitable as starting materials. So you can z. B. the mercaptophosphonic acid esters (in which - X - according to the general formula given above is the direct bond between the radical R 2 and the phosphorus atom) easily by reaction of chloroalkyl

alkylsulfiden mit Natrium-Dialkylphosphiten erhalten. Diese Reaktion verläuft nach folgendem Schema:obtained alkyl sulfides with sodium dialkyl phosphites. This reaction proceeds according to the following scheme:

,OR, OR

R-S-(CH2)^-ClRS- (CH 2 ) ^ - Cl

,OR, OR

> R — S — (CH2L^- P' + NaCl > R - S - (CH 2 L ^ - P '+ NaCl

OROR

Die Merkaptoester der Thiolphosphorsäure sind ζ. Β. aus Chloralkyl-alkylsulfiden und den Alkali- oder Ammoniumsalzen der O, O-Dialkylthiol-phosphorsäure zugänglich.The mercaptoesters of thiol phosphoric acid are ζ. Β. from chloroalkyl-alkyl sulfides and the alkali or Ammonium salts of O, O-dialkylthiol-phosphoric acid accessible.

|| /OR|| / OR

R — S — (CH2L,- Cl + NH4S-P ( >R - S - (CH 2 L, - Cl + NH 4 SP (>

R_S— CH2L-S-P R _S- CH 2 LSP

Die isomeren Merkaptoester der Thionophosphorsäure mit vertauschter Stellung von O- und S-Atom können z. B. nach den Angaben der deutschen Patentschrift 836 349 erhalten werden.The isomeric mercaptoesters of thionophosphoric acid with the position of O and S atoms interchanged can e.g. B. can be obtained according to the information in German Patent 836,349.

Es ist bekannt, daß Merkaptogruppen enthaltende Phosphorsäure- bzw. Thiophosphorsäureester hydrolytisch spaltbar und gegen Oxydationsmittel empfindlich sind. Durch Austausch des am Phosphor doppelt gebundenen Schwefels gegen Sauerstoff durch Einwirkung von Oxydationsmitteln werden die entsprechenden Phosphor-Sauerstoff-Verbindungen erhalten. Daß sich die thioätherhaltigen Phosphorsäureester nun in glatter Reaktion mit Wasserstoffsuperoxyd einheitlich zu den gewünschten Sulfoxyden oxydieren lassen, ist erstaunlich und konnte in keiner Weise vorausgesehen werden.It is known that phosphoric acid esters or thiophosphoric acid esters containing mercapto groups hydrolytically are fissile and sensitive to oxidizing agents. By replacing the phosphorus twice bound sulfur against oxygen by the action of oxidizing agents become the corresponding Phosphorus-oxygen compounds obtained. That the thioether-containing phosphoric acid esters now in smooth reaction with hydrogen peroxide uniformly to the desired sulfoxides oxidize is amazing and could not be foreseen in any way.

Die Oxydation der thioätherhaltigen Phosphorsäure- bzw. Thiophosphorsäureester wird am besten in wassermischbaren organischen Lösungsmitteln durchgeführt. Wie sich weiter zeigte, ist überraschenderweise als Lösungsmittel bei der Oxydation der Alkohol besonders geeignet, der als O-Alkylrest in den betreffenden Phosphorsäureestern vorhanden ist. Bei O-Methylestern ist daher am besten Methanol, beiThe oxidation of the thioether-containing phosphoric or thiophosphoric acid esters is best carried out in water-miscible organic solvents. As it turned out, is surprising particularly suitable as a solvent in the oxidation of alcohol, which is present as an O-alkyl radical in the concerned phosphoric acid esters is present. In the case of O-methyl esters, methanol is therefore best

O-Äthylestern Äthanol als Lösungsmittel zu verwenden. Es können aber auch andere Lösungsmittel, z. B. Eisessig, Aceton usw., Verwendung finden.O-ethyl ester to use ethanol as a solvent. But it can also use other solvents such. B. glacial acetic acid, acetone, etc., find use.

Für die Oxydation sind am geeignetsten milde Temperaturen (Raumtemperatur bis'etwa 60°). Verbraucht wird zur Oxydation genau 1 Mol Wasserstoffsuperoxyd (z. B. in Form von »Perhydrok) auf ι Mol thioätherhaltigen Phosphorsäureester. Ein Überschuß an Wasserstoffperoxyd ist bei der Oxydation thioätherhaltiger Phosphorsäureester nicht schädlich, stört jedoch bei der Oxydation thioätherhaltiger Thiophosphorsäureester aus den oben beschriebenen Gründen des Ersatzes von Schwefel durch Sauerstoff.Mild temperatures (room temperature to about 60 °) are most suitable for the oxidation. Consumed exactly 1 mole of hydrogen peroxide is used for oxidation (e.g. in the form of »Perhydrok) on ι mol of thioether-containing phosphoric acid ester. An excess of hydrogen peroxide is involved in oxidation Thioether-containing phosphoric acid ester is not harmful, but interferes with the oxidation of thioether-containing Thiophosphoric acid ester for the reasons described above of replacing sulfur with Oxygen.

Die nach dem neuen Verfahren erstmalig erhaltenen sulfoxydgruppenhaltigen Phosphorsäureester haben gegenüber den Merkaptogruppen enthaltenden Estern folgende Eigenschaften.Those obtained for the first time using the new process Phosphoric acid esters containing sulfoxide groups have compared to the esters containing mercapto groups following properties.

Sie sind weitgehend wassermischbar bis wasserlöslich, und sie sind in sauren bis neutralen Medien gegen hydrolytische Einflüsse weitgehend unempfindlieh. They are largely water-miscible to water-soluble, and they are largely insensitive to hydrolytic influences in acidic to neutral media.

Überaus wertvoll werden diese neuen Sulfoxyde dadurch, daß sie gegenüber den Ausgangsmaterialien .eine gesteigerte insektizide Wirkung innertherapeutischer Art zeigen. Diese Wirkung ist im Vergleich zu den Ausgangsmaterialien langer anhaltend, da die Sulfoxydester gegen Hydrolyseeinflüsse beständiger sind. Die folgenden Beispiele sollen den Umfang dej: Erfindung erläutern.These new sulfoxides become extremely valuable in that they are more valuable than the starting materials . an increased insecticidal effect within therapeutic Kind of show. This effect is longer lasting compared to the starting materials, there the sulfoxide esters are more resistant to the effects of hydrolysis. The following examples are intended to illustrate the scope dej: Explain the invention.

Beispiel 1example 1

C2H5-SO-CH2-CH2-O-P:C 2 H 5 -SO-CH 2 -CH 2 -OP:

,0CH5 , 0CH 5

'OC2H5 'OC 2 H 5

17 g Thionophosphorsäure-O, 0-diäthyl-0-/5-merkaptoäthylester werden in 20 ecm Äthanol gelöst. Zu der Lösung tropft man bei 35 bis 400 6,5 ecm 36°/0iges Wasserstoffperoxyd. Nach Abklingen der Reaktion, während der leicht gekühlt werden muß, wird 2 Stunden bei 400 weitergerührt. In der klaren neutralen Lösung ist jetzt noch wenig freies Wasserstoffperoxyd nachweisbar, das aber bei der anschließenden Fraktionierung verschwindet. Man erhält bei der Destillation im Hochvakuum 12 bis 14 g des Sulfoxydesters vom Kp.OiO1 950. Ausbeute: 64 bis 74% der Theorie, Der Ester ist begrenzt wasserlöslich.17 g of thionophosphoric acid 0, 0-diethyl-0- / 5-mercaptoethyl ester are dissolved in 20 ecm of ethanol. To the solution is added dropwise at 35 to 40 0 6.5 cc of 36 ° / 0 sodium hydrogen peroxide. After the reaction has to be, while the slightly cooled, 2 hours at 40 0 is further stirred. Little free hydrogen peroxide can still be detected in the clear, neutral solution, but this disappears during the subsequent fractionation. Obtained in the distillation in a high vacuum of 12 to 14 g of boiling Sulfoxydesters. OiO1 95 0th Yield: 64 to 74% of theory. The ester has limited water solubility.

Beispiel 2Example 2

,OC2H5 , OC 2 H 5

OC2H5 OC 2 H 5

52 g Thiolphosphorsäure-O, O-diäthyl-S-^-äthylmerkaptoäthylester werden in 50 ecm Methanol gelöst und, ■ wie oben beschrieben, mit 20 ecm Wasserstoffperoxyd oxydiert. Nach dem Fraktionieren im Hochvakuum erhält man den Sulfoxydester als wassermischbares Öl vom Kp.0)01 io8° in einer Ausbeute von 40 bis 45 g = 69 bis 78 % der Theorie.52 g of thiolphosphoric acid O, O-diethyl-S - ^ - äthylmercaptoethylester are dissolved in 50 ecm of methanol and, as described above, oxidized with 20 ecm of hydrogen peroxide. After fractionating under high vacuum 0) 01 ° io8 one obtains the Sulfoxydester as the water-oil, bp. In a yield of 40 to 45 g = 69-78% of theory.

Beispiel 3Example 3

C2H5-SO-CH2-CH2-O-P;C 2 H 5 -SO-CH 2 -CH 2 -OP;

,OCH,, OCH,

"OCH,"OCH,

20 g Thionophosphorsäure-O, O-dimethyl-0-/?- äthylmerkaptoäthylester werden in 20 ecm Methanol,20 g thionophosphoric acid-O, O-dimethyl-0 - /? - Ethylmercaptoethylester are dissolved in 20 ecm of methanol,

wie in den vorigen Beispielen beschrieben, mit 8,5 ecm 36°/0igem Wasserstoffperoxyd oxydiert. Nach der üblichen Aufarbeitung erhält man 14 g = 66 °/0 der Theorie an Sulfoxydester vom Kp.0;0195 bis 960. Die Substanz ist begrenzt wasserlöslich.as described in the previous examples, oxidized with 8.5 cc of 36 ° / 0 sodium hydrogen peroxide. After the usual workup 14 g = 66 ° / 0 of the theoretical obtained at Sulfoxydester, bp 0;. 01 95 to 96 0. The substance has limited water solubility.

Beispiel 4Example 4

-so—CH2-CH9-s—p;-so-CH 2 -CH 9 -s-p;

,0CH5 , 0CH 5

OCH.,OCH.,

46 g Thiolphosphorsaure-O, O-dimethyl-S-^-äthylmerkaptoäthylester werden in der üblichen Weise in 50 ecm Methanol mit 20 ecm 4O°/0igem Wasserstoffperoxyd oxydiert und, wie in den vorigen Beispielen beschrieben, aufgearbeitet. Das Präparat ist wassermischbar. Man erhält den Sulfoxydester in einer Aus46 g Thiolphosphorsaure-O, O-dimethyl-S - ^ - äthylmerkaptoäthylester be oxidized in the usual manner in 50 cc of methanol with 20 cc of 4O ° / 0 hydrogen peroxide and sodium, as described in the previous examples, worked up. The preparation is water-miscible. The sulfoxide ester is obtained in one go

beute von 65 bis 75% der Theorie, Kp.OiO1 etwa 105 20 bis 106°.yield from 65 to 75% of theory, b.p. OiO1 about 105 20 to 106 °.

Claims (1)

PATENTANSPRUCH:PATENT CLAIM: Verfahren zur Herstellung von Sulfoxydgruppen enthaltenden Estern der Phosphor- oder Thiophosphorsäuren, dadurch gekennzeichnet, daß Phosphorsäureester der allgemeinen FormelProcess for the preparation of esters of phosphoric or thiophosphoric acids containing sulfoxide groups, characterized in that phosphoric acid esters of the general formula O (S)O (S) Il ,OR3 Il , OR 3 R1-S-R2-X-P^R 1 -SR 2 -XP ^ OR11 OR 11 worin R1 ein Alkyl-, Aralkyl- oder Arylrest, R2 ein organischer Rest, X = O oder S bedeutet oder eine direkte Bindung zwischen dem Rest R2 und dem Phosphoratom ist und R3 und R4 beliebige Alkylreste sind, in geeigneten wassermischbaren Lösungsmitteln mit Wasserstoffperoxyd oxydiert werden.where R 1 is an alkyl, aralkyl or aryl radical, R 2 is an organic radical, X = O or S or is a direct bond between the radical R 2 and the phosphorus atom and R 3 and R 4 are any alkyl radicals, in suitable water-miscible ones Solvents are oxidized with hydrogen peroxide. 9 509 659/66 2.56 (609 584 8.56)9 509 659/66 2.56 (609 584 8.56)
DEF16085A 1954-11-06 1954-11-07 Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups Expired DE947368C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEF16085A DE947368C (en) 1954-11-06 1954-11-07 Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DEF21822A DE1039511B (en) 1954-11-06 1954-11-06 Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups
DE338442X 1954-11-06
DEF16085A DE947368C (en) 1954-11-06 1954-11-07 Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1039511B (en) * 1954-11-06 1958-09-25 Bayer Ag Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups
DE1063153B (en) * 1956-12-10 1959-08-13 Bayer Ag Process for the preparation of esters of thiophosphoric acid containing sulfide, sulfoxide or sulfone groups
US2910501A (en) * 1957-01-05 1959-10-27 Bayer Ag Thiophosphoric acid esters and process for their manufacture
DE1078124B (en) * 1957-06-18 1960-03-24 Bayer Ag Process for the preparation of thionophosphonic acid esters
DE1083810B (en) * 1956-12-10 1960-06-23 Bayer Ag Process for the preparation of esters of thiophosphoric acid containing sulfoxide or sulfonic groups
DE1091102B (en) * 1956-11-22 1960-10-20 Boehringer Sohn Ingelheim Process for the preparation of phosphoric or thiophosphoric acid esters containing sulfoxyl or sulfonyl groups
US2960523A (en) * 1957-12-19 1960-11-15 Rohm & Haas Dialkylphosphatoalkyl vinyl sulfides
DE1114671B (en) * 1956-11-22 1961-10-05 Boehringer Sohn Ingelheim Pest repellants
DE1117110B (en) * 1957-06-14 1961-11-16 Bayer Ag Process for the preparation of thionophosphoric acid esters
DE1139496B (en) * 1959-03-13 1962-11-15 Bayer Ag Process for the preparation of aryl-alkyl-thiolphosphinic acid esters
DE1147227B (en) * 1961-06-08 1963-04-18 Bayer Ag Process for the production of thio- or dithiophosphorus (- phosphonic, -phosphine) acid esters
US6818670B2 (en) 1999-11-09 2004-11-16 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US6900190B2 (en) 2000-03-28 2005-05-31 Bayer Aktiengesellschaft Active substance combinations having insecticidal and acaricidal properties
DE102007045955A1 (en) 2007-09-26 2009-04-09 Bayer Cropscience Ag Active agent combination, useful e.g. for combating animal pests and treating seeds of transgenic plants, comprises substituted amino-furan-2-one compound and at least one compound e.g. diazinon, isoxathion, carbofuran or aldicarb

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1039511B (en) * 1954-11-06 1958-09-25 Bayer Ag Process for the preparation of esters of phosphoric and thiophosphoric acids containing sulfoxide groups
DE1091102B (en) * 1956-11-22 1960-10-20 Boehringer Sohn Ingelheim Process for the preparation of phosphoric or thiophosphoric acid esters containing sulfoxyl or sulfonyl groups
DE1114671B (en) * 1956-11-22 1961-10-05 Boehringer Sohn Ingelheim Pest repellants
DE1063153B (en) * 1956-12-10 1959-08-13 Bayer Ag Process for the preparation of esters of thiophosphoric acid containing sulfide, sulfoxide or sulfone groups
DE1083810B (en) * 1956-12-10 1960-06-23 Bayer Ag Process for the preparation of esters of thiophosphoric acid containing sulfoxide or sulfonic groups
US2910501A (en) * 1957-01-05 1959-10-27 Bayer Ag Thiophosphoric acid esters and process for their manufacture
DE1117110B (en) * 1957-06-14 1961-11-16 Bayer Ag Process for the preparation of thionophosphoric acid esters
DE1078124B (en) * 1957-06-18 1960-03-24 Bayer Ag Process for the preparation of thionophosphonic acid esters
US2960523A (en) * 1957-12-19 1960-11-15 Rohm & Haas Dialkylphosphatoalkyl vinyl sulfides
DE1139496B (en) * 1959-03-13 1962-11-15 Bayer Ag Process for the preparation of aryl-alkyl-thiolphosphinic acid esters
DE1147227B (en) * 1961-06-08 1963-04-18 Bayer Ag Process for the production of thio- or dithiophosphorus (- phosphonic, -phosphine) acid esters
US6818670B2 (en) 1999-11-09 2004-11-16 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US6900190B2 (en) 2000-03-28 2005-05-31 Bayer Aktiengesellschaft Active substance combinations having insecticidal and acaricidal properties
DE102007045955A1 (en) 2007-09-26 2009-04-09 Bayer Cropscience Ag Active agent combination, useful e.g. for combating animal pests and treating seeds of transgenic plants, comprises substituted amino-furan-2-one compound and at least one compound e.g. diazinon, isoxathion, carbofuran or aldicarb

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