DE1254154B - Process for the preparation of dithiophosphorus (- phosphine -) - acid esters - Google Patents

Process for the preparation of dithiophosphorus (- phosphine -) - acid esters

Info

Publication number
DE1254154B
DE1254154B DEF35076A DEF0035076A DE1254154B DE 1254154 B DE1254154 B DE 1254154B DE F35076 A DEF35076 A DE F35076A DE F0035076 A DEF0035076 A DE F0035076A DE 1254154 B DE1254154 B DE 1254154B
Authority
DE
Germany
Prior art keywords
dithiophosphorus
acid esters
preparation
phosphinic
phosphine
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
Application number
DEF35076A
Other languages
German (de)
Inventor
Dr Walter Lorenz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
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 to GB970905D priority Critical patent/GB970905A/en
Priority to NL284043D priority patent/NL284043A/xx
Priority to NL135954D priority patent/NL135954C/xx
Priority to BE623227D priority patent/BE623227A/xx
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF35076A priority patent/DE1254154B/en
Priority to CH1124762A priority patent/CH421123A/en
Priority to FR911434A priority patent/FR1335759A/en
Priority to BR14362562A priority patent/BR6243625D0/en
Publication of DE1254154B publication Critical patent/DE1254154B/en
Pending legal-status Critical Current

Links

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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650905—Six-membered rings having the nitrogen atoms in the positions 1 and 2
    • C07F9/650947—Six-membered rings having the nitrogen atoms in the positions 1 and 2 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
    • A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
    • A01N57/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing heterocyclic radicals

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.:Int. Cl .:

Deutsche Kl.:German class:

C07dC07d

PESTPEST

Nummer: 1 254 154Number: 1 254 154

Aktenzeichen: F 35076 IV d/12 ρFile number: F 35076 IV d / 12 ρ Anmcldetag: 7. Oktober 1961Registration date: October 7, 1961 Auslegetag: 16. November 1967Opened on: November 16, 1967

Die Erfindung betrifft ein Verfahren 2ur Herstellung von Dithiophosphor-(-phosphin-)-säureestern, das dadurch gekennzeichnet ist, daß man 2-ChIormethyl-phthalazon-(l) mit Salzen von Dialkylthionothiolphosphor-(-phosphin-)-säuren der allgemeinenThe invention relates to a process 2ur production of dithiophosphorus (- phosphine -) - acid esters, which is characterized in that 2-chloromethyl-phthalazon- (l) with salts of dialkylthionothiolphosphorus - (- phosphinic -) - acids of the general Formelformula

'X-Ri'X-Ri

HS — P;HS - P;

IOIO

in der X ein Sauerstoffatom oder eine direkte Bindung und Ri und R2 niedermolekulare Alkylreste bedeuten, in an sich bekannter Weise umsetzt. Es werden auf diese Weise insektizid wirksame Verbindungen der allgemeinen Formelin which X is an oxygen atom or a direct bond and Ri and R 2 are low molecular weight alkyl radicals, is reacted in a manner known per se. In this way, insecticidally active compounds of the general formula are obtained

S N-CH2-S-P^S N-CH 2 -SP ^

X-R2 XR 2

2020th

erhalten, in welcher X, Ri und R2 die oben angegebene Bedeutung haben.obtained, in which X, Ri and R 2 have the meaning given above.

Dithiophosphorsäureester des 3-Methylolbenztriazinons-(4) erhält man nach den Angaben der deutschen Patentschrift 927 270 durch Kondensation von 3-Chlormethylbenztriazinon-(4) mit den Salzen der entsprechenden Ο,Ο-Dialkyldithiophosphorsäuren. Aus der Reihe dieser VerbindungenDithiophosphoric acid ester of 3-Methylolbenztriazinons- (4) is obtained according to the information German Patent 927 270 by condensation of 3-chloromethylbenztriazinon- (4) with the Salts of the corresponding Ο, Ο-dialkyldithiophosphoric acids. From the series of these connections Verfahren zur Herstellung von Dithiophosphor-(-phosphin-)-säureesternProcess for the production of Dithiophosphorus (- phosphinic) acid esters

Anmelder:Applicant:

Farbenfabriken Bayer Aktiengesellschaft,Paint factories Bayer Aktiengesellschaft, LeverkusenLeverkusen Als Erfinder benannt:Named as inventor: Dr. Walter Lorenz, Wuppertal-VohwinkelDr. Walter Lorenz, Wuppertal-Vohwinkel

ist besonders der Ο,Ο-Dimethyldithiophosphorsäureester als wertvolles Insektizides Mittel bekanntgeworden.the Ο, Ο-dimethyldithiophosphoric acid ester in particular has become known as a valuable insecticidal agent.

Die erfindungsgcmäß herstellbaren Verbindungen besitzen eine bessere Thermostabilität als die bekannten Dithiophosphorsäureester des 3-Methylolbcnztriazinons-(4). Die Wirksamkeit der neuen Ester gegen Blattläuse und Spinnmilben ist hervorragend. Sie zeigen ferner eine bessere ovizide Wirkung bei Spinnmilben und eine bessere Wirkung gegen Fliegenmaden und Wanderheuschrecken als vergleichbare Verbindungen des Standes der Technik. Diese unerwartete, technische Überlegenheit der Verfahrensprodukte geht aus den im folgenden tabellarisch zusammengestellten Ergebnissen von Vergleichsversuchen hervor:The compounds that can be produced according to the invention have a better thermal stability than the known dithiophosphoric acid esters of 3-Methylolbcnztriazinons- (4). The effectiveness of the new Ester against aphids and spider mites is excellent. They also show a better ovicidal effect in spider mites and a better action against fly maggots and locusts than comparable compounds of the prior art. This unexpected, technical superiority of the process products results from the following Results of comparative tests compiled in tabular form:

Verbindung (Konstitution)Connection (constitution) Warmbtöter-Warm-killer

toxizität (DLm toxicity (DLm

Ratte per osRat per os

in mg/kg)in mg / kg)

Insektizide und akarizide WirkungInsecticidal and acaricidal effects Anwendung gegenApplication against

WirkstoffkonzentmüonActive ingredient concentration

Abtötung derKilling the SchädlingePests

in 1Voin 1 Vo

CO \CO \

N NN N

CH2-S-P(OCHa)2 CH 2 -SP (OCHa) 2

400400

FliegenmadenFly maggots

0,1 0,010.1 0.01

100 90100 90

CH' (verfahrensgemäß, Beispiel 1)CH ' (according to the procedure, example 1)

COx CO x

N — CH2 — S — P(OCH^)2 N - CH 2 - S - P (OCH ^) 2 FüegeiunadenFüegeiunaden

0,1« 0,010.1 « 0.01

60 060 0

(bekannt)(known)

704 Mt/407704 m / 407

Fortsetzungcontinuation

Verbindung (Konstitution)Connection (constitution)

COx IlCO x Il

N — CH2 — S — P(OOH5)*N - CH 2 - S - P (OOH 5 ) *

N
CH'N
CH '

(verfahrensgemäß, Beispiel 2)(according to the procedure, example 2)

S
II
N — CH2 — S — P(OQHo)2 S.
II
N - CH 2 - S - P (OQHo) 2

N
(bekannt)N
(known)

CO\CO \

Warmblüter-Warm-blooded

toxizität (DLv)toxicity (DLv)

Ratte per osRat per os

in mg/kg)in mg / kg)

IlIl

N — CH2 — S — P(C2Hs)2 N - CH 2 - S - P (C 2 Hs) 2

(verfahrensgemäß, Beispiel 3)(according to the procedure, example 3)

N-CH2-S-P(CHj)2 N-CH 2 -SP (CHj) 2

(bekannt)(known)

1000 Insektizide und akarizide Wirkung1000 insecticidal and acaricidal effects

Anwendung gegenApplication against

Wanderheuschrecken Migratory locusts

Wirkstoffkonzentration
in "A, Active ingredient concentration
in "A,

0,1
0,010.1
0.01

Wanderheuschrecken Migratory locusts

FliegenmadenFly maggots

FliegenmadenFly maggots

0,1
0,010.1
0.01

0.1
0,010.1
0.01

0,1
0,010.1
0.01

Abtölung derMortification of the

SchädlingePests

in 0 Ai in 0 Ai

100
90100
90

70 070 0

100
100100
100

80
080
0

Beispiel 1example 1

COx CO x

N — CH2 — S — P(OCHs)2 N - CH 2 - S - P (OCHs) 2

39 g (0,2 Mol) 2 - Ch,lormethylphthalazon - (1), Fp. 14O0C, und 42 g (0,24MoI) des Ammoniumsalzes der O,0-Dimethyldithiophosphorsäure werden in 150 ecm Aceton 1 Stunde auf 50 bis 60°C erwärmt. Nach dem Erkalten der Mischung versetzt man diese mit Wasser, bis kein weiterer Niederschlag mehr entsteht. Das ausgeschiedene Kristallisat wird abgesaugt und mit Wasser gewaschen. Durch Umkristallisieren aus Isopropylalkohol (1 g auf 5 ecm) erhält man den Ο,Ο-Dimethyldithiophosphorsäureester des 2-Methylolphthalazons-(l) in farblosen Nädclchen vom Schmelzpunkt 870C. Die Ausbeute beträgt 55 g (87.1(l/o der Theorie).39 g (0.2 mol) of 2 - Ch, lormethylphthalazon - (1), melting point 14O 0 C, and 42 g (0.24 mol) of the ammonium salt of O, 0-dimethyldithiophosphoric acid are in 150 ecm acetone to 50 to 1 hour 60 ° C heated. After the mixture has cooled down, water is added until no further precipitate forms. The precipitated crystals are filtered off with suction and washed with water. Recrystallization from isopropyl alcohol (1 g in 5 cc), one obtains the Ο, Ο-Dimethyldithiophosphorsäureester of 2-Methylolphthalazons- (l) in colorless Nädclchen a melting point of 87 0 C. The yield is 55 g (87. 1 (l / o of Theory).

Molgewicht 316,3:Molar weight 316.3:

Berechnet ... P 9,78, S 20,05, N 8,96%;
gefunden ... P 9,48, S 20,27, N 8,93%.Calculated ... P 9.78, S 20.05, N 8.96%;
found ... P 9.48, S 20.27, N 8.93%.

Bereits von 0,01%igen Lösungen des Produktes werden Blattläuse zu 60 und Spinnmilben sogar zu 9O°/o abgetötet. Gegen letztgenannte Schädlinge besitzt das Präparat außerdem eine ovizide Wirkung.Even from 0.01% solutions of the product, aphids turn up to 60 and spider mites even turn up 90 per cent killed. The preparation also has an ovicidal effect against the latter pests.

Das als Ausgangsmaterial benötigte 2-Chlormethylphthalazon-(l) kann beispielsweise wie folgt hergestellt werden:The 2-chloromethylphthalazone (l) required as starting material can be made, for example, as follows:

59 g (0,4 Mol) Phthalazon (Fp. 1840C) und 13,2 g (0,44 Mol) Paraformaldehyd werden in 200 ecm59 g (0.4 mol) phthalazone (mp. 184 0 C) and 13.2 g (0.44 mol) of paraformaldehyde are suspended in 200 cc

Chloroform suspendiert. Zur Depolymerisation des Paraformaldehyds fügt man 5 g p-Toluolsulfosäure zu der Mischung und rührt diese über Nacht bei Raumtemperatur. Am anderen Morgen wird das Reaktionsgemisch bei 25 bis 3O0C unter Außenkühlung mit 58,5 g (0,486MoI) Thionylchlorid (35 ecm) versetzt und anschließend Va Stunde auf 6O0C erwärmt. Nach dem Erkalten der Mischung saugt man die geringe Menge zurückgebildeten Phthalazone ab. Das Filtrat wird zunächst mit Wasser und mit 2 η-Natronlauge gewaschen, um teerige Anteile zu entfernen. Schließlich wäscht man es mit Wasser bis zur neutralen Reaktion, trocknet die organische Schicht über Natriumsulfat und destilliert das Lösungsmittel ab. Als Rückstand hinterbleibcn 54,5 g (70% der Theorie) einer bräunlichen Kristallmasse vom Schmelzpunkt 139°C. Durch Umkristallisieren aus Isopropylalkohol erhält man das 2-Chlormethylphthalazon-(t) in nahezu farblosen Kristallen, die bei 141 bis 142°C schmelzen.Suspended in chloroform. To depolymerize the paraformaldehyde, 5 g of p-toluenesulfonic acid are added to the mixture and the mixture is stirred overnight at room temperature. The next morning the reaction mixture at 25 to 3O 0 C with external cooling with 58.5 g (0,486MoI) of thionyl chloride is added (35 cc) and then heated at 6O 0 C Va hour. After the mixture has cooled down, the small amount of phthalazones that have formed back is filtered off with suction. The filtrate is first washed with water and with 2η sodium hydroxide solution in order to remove tarry components. Finally, it is washed with water until it is neutral, the organic layer is dried over sodium sulfate and the solvent is distilled off. The residue left behind is 54.5 g (70% of theory) of a brownish crystal mass with a melting point of 139 ° C. Recrystallization from isopropyl alcohol gives 2-chloromethylphthalazone- (t) in almost colorless crystals which melt at 141 to 142 ° C.

Molgewicht 194,6:Molar weight 194.6:

Berechnet ... N 14,53, Cl 18,22%;
gefunden ... N 14,31, Cl 18,23<>/o-Calculated ... N 14.53, Cl 18.22%;
found ... N 14.31, Cl 18.23 <> / o-

COx CO x

Beispiel 2 Example 2

N — CH2 — S — P(OCiH.-,)_>N - CH 2 - S - P (OCiH .-,) _>

39 g (0,2MoI) 2-Chlormethylphthala7.on-(l) und 49 g (0,24 Mol) des Ammoniumsalzes der Diäthyldithiophosphorsäure werden in 150 ecm Aceton 1 Stunde bei 50 bis 60 C erwärmt. Nach Erkalten setzt man 250 ecm Wasser zu und rührt, bis das ausgefallene öl erstarrt. Es wird abgesaugt und mit Wasser gewaschen. Aus lsopropylalkohol (I : 1) kristallisiert der O.O-Diäthyldithiophosphorsäureester des 2-Methylolphthalazons-(l) in farblosen Nädelchen vom Fp. 58C Ausbeute 64 g (93,3% der Theorie).39 g (0.2 mol) of 2-chloromethylphthala7.on- (l) and 49 g (0.24 mol) of the ammonium salt of diethyldithiophosphoric acid are heated in 150 ecm acetone for 1 hour at 50 to 60 C. After cooling down 250 ecm of water are added and the mixture is stirred until the precipitated oil solidifies. It is sucked off and with Water washed. The O.O-diethyldithiophosphoric acid ester crystallizes from isopropyl alcohol (I: 1) of 2-methylolphthalazone- (l) in colorless needles with a melting point of 58C, yield 64 g (93.3% the theory).

Molgewicht 344,4:Molar weight 344.4:

Berechnet ... P 9,00, S 18,62. N 8,14%,;
gefunden ... P 8,66, S 18,90. N 8,26%.Calculated ... P 9.00, S 18.62. N 8.14%;
found ... P 8.66, S 18.90. N 8.26%.

Wirksamkeiteffectiveness Blattläuse | SpinnmilbenAphids | Spider mites

ovizide Wirkungovicidal effect

phosphinsäure werden in 150 ecm Aceton 1 Stunde auf 50 bis 60"C erwärmt. Nach Erkalten setzt man ecm Wasser zu und rührt, bis das ausgefallene öl erstarrt ist. Das Kristallisat saugt man ab und wäscht es mit Wasser nach. Aus Methanol erhält man den Diäthyldithiophosphinsäureester des 2-Methylolphlhalazons-(l) rein in Form farbloser Kristalle vom Fp. 900C. Ausbeute 55 g (88.6% der Theorie).phosphinic acid are heated in 150 ecm acetone for 1 hour to 50 to 60 ° C. After cooling, ecm water is added and the mixture is stirred until the precipitated oil has solidified. The crystallizate is filtered off with suction and washed with water. The methanol is obtained Diäthyldithiophosphinsäureester of 2-Methylolphlhalazons- (l) purely in the form of colorless crystals of mp. 90 0 C. yield 55 g (88.6% of theory).

Molgewicht 312,4:Molecular weight 312.4:

Berechnet ... P 9,92, S 20,53. N 8.97%;
gefunden ... P 10,19, S 20,61, N 9,04%.Calculated ... P 9.92, S 20.53. N 8.97%;
found ... P 10.19, S 20.61, N 9.04%.

0,01 »/ο0.01 »/ ο

100% j 0,01'Vo100% j 0.01'Vo

100»/»100 »/»

Beispiel 3Example 3

COx CO x

N — CH2 — S —N - CH 2 - S -

3535

Wirksamkeiteffectiveness

BlattläuseAphids

0,1%0.1%

50%50%

SpinnmilbenSpider mites

0,1%0.1%

90%90%

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von Dithiophosphor-(-phosphin-)-säureestcrn, dadurch gekennzeichnet, daß man 2-Chlormcthylphthalazon-(l) mit Salzen von Dialkylthionothiolphosphot-(-phosphin-)-säuren der allgemeinen FormelProcess for the preparation of dithiophosphorus (- phosphinic) - acid esters, characterized in that 2-chloromethylphthalazone (l) with salts of dialkylthionothiolphosphot (- phosphinic) acids the general formula HS-P:HS-P: ,X-Ri, X-Ri — R2 - R 2 in der X ein Sauerstoffatom oder eine direkte Bindung und Ri und R2 niedermolekulare Alkylrestc bedeuten, in an sich bekannter Weise umsetzt.in which X is an oxygen atom or a direct bond and Ri and R 2 are low molecular weight alkyl radicals, in a manner known per se. 39 g (0,2MoI) 2-Chlormethylphthalazon-(l) und 42 g (0,24 Mol) des Kaliumsalzes der Diäthyldithio-In Betracht gezogene Druckschriften:
Deutsche Patentschriften Nr. 927 270, 933 627; deutsche Auslegeschriften Nr. 1099 533.1 102150, 852;
österreichische Patentschrift Nr. 213 905.39 g (0.2MoI) of 2-chloromethylphthalazone- (l) and 42 g (0.24 mol) of the potassium salt of diethyldithio-Publications considered:
German Patent Nos. 927 270, 933 627; German Auslegeschriften Nos. 1099 533.1 102150, 852;
Austrian patent specification No. 213 905. 709 5*8/407 11. «7709 5 * 8/407 11. «7 Bundesdruckerei BerlinBundesdruckerei Berlin
DEF35076A 1961-10-07 1961-10-07 Process for the preparation of dithiophosphorus (- phosphine -) - acid esters Pending DE1254154B (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
GB970905D GB970905A (en) 1961-10-07
NL284043D NL284043A (en) 1961-10-07
NL135954D NL135954C (en) 1961-10-07
BE623227D BE623227A (en) 1961-10-07
DEF35076A DE1254154B (en) 1961-10-07 1961-10-07 Process for the preparation of dithiophosphorus (- phosphine -) - acid esters
CH1124762A CH421123A (en) 1961-10-07 1962-09-25 Process for the preparation of thiophosphorus (on, in) acid esters
FR911434A FR1335759A (en) 1961-10-07 1962-10-05 New insecticidal compositions for use in agriculture
BR14362562A BR6243625D0 (en) 1961-10-07 1962-10-05 PROCESS OF PRODUCTION OF ESTERS OF THIOPHOSPHORIC ACID THIOPHOSPHONIC AND THIOPHOSPHINIC ACID AND COMPOSITES BASED ON THEM

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF35076A DE1254154B (en) 1961-10-07 1961-10-07 Process for the preparation of dithiophosphorus (- phosphine -) - acid esters

Publications (1)

Publication Number Publication Date
DE1254154B true DE1254154B (en) 1967-11-16

Family

ID=7095840

Family Applications (1)

Application Number Title Priority Date Filing Date
DEF35076A Pending DE1254154B (en) 1961-10-07 1961-10-07 Process for the preparation of dithiophosphorus (- phosphine -) - acid esters

Country Status (6)

Country Link
BE (1) BE623227A (en)
BR (1) BR6243625D0 (en)
CH (1) CH421123A (en)
DE (1) DE1254154B (en)
GB (1) GB970905A (en)
NL (2) NL135954C (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2316821A1 (en) * 1973-04-04 1974-10-17 Bayer Ag S- SQUARE CLIP ON 1,6-DIHYDRO-6OXO-PYRIDAZINE- (1) YLMETHYL SQUARE CLAMP FOR - (THIONO) - (DI) -THIOL-PHOSPHORUS (PHOSPHONE) ACID ESTER OR. -ESTERAMIDE DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES, ACARICIDES AND NEMATICIDES

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE927270C (en) * 1953-02-26 1955-05-02 Bayer Ag Process for the preparation of thiophosphoric acid esters
DE933627C (en) * 1953-02-10 1955-09-29 Bayer Ag Process for the preparation of thiophosphoric acid esters
DE1099533B (en) * 1959-05-02 1961-02-16 Bayer Ag Process for the preparation of dithio- or thiolphosphorus, -phosphonic or -phosphinic acid esters
AT213905B (en) * 1958-12-30 1961-03-10 Albert Ag Chem Werke Process for the preparation of new thiol or thionothiol phosphoric acid esters
DE1102150B (en) * 1959-05-09 1961-03-16 Bayer Ag Process for the preparation of thiophosphonic or thiophosphinic acid esters
DE1112852B (en) * 1958-03-18 1961-08-17 Bayer Ag Pest repellants

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE933627C (en) * 1953-02-10 1955-09-29 Bayer Ag Process for the preparation of thiophosphoric acid esters
DE927270C (en) * 1953-02-26 1955-05-02 Bayer Ag Process for the preparation of thiophosphoric acid esters
DE1112852B (en) * 1958-03-18 1961-08-17 Bayer Ag Pest repellants
AT213905B (en) * 1958-12-30 1961-03-10 Albert Ag Chem Werke Process for the preparation of new thiol or thionothiol phosphoric acid esters
DE1099533B (en) * 1959-05-02 1961-02-16 Bayer Ag Process for the preparation of dithio- or thiolphosphorus, -phosphonic or -phosphinic acid esters
DE1102150B (en) * 1959-05-09 1961-03-16 Bayer Ag Process for the preparation of thiophosphonic or thiophosphinic acid esters

Also Published As

Publication number Publication date
GB970905A (en)
NL135954C (en)
BR6243625D0 (en) 1973-05-17
NL284043A (en)
BE623227A (en)
CH421123A (en) 1966-09-30

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