CH294598A - Process for producing a phosphoric acid ester. - Google Patents

Process for producing a phosphoric acid ester.

Info

Publication number
CH294598A
CH294598A CH294598DA CH294598A CH 294598 A CH294598 A CH 294598A CH 294598D A CH294598D A CH 294598DA CH 294598 A CH294598 A CH 294598A
Authority
CH
Switzerland
Prior art keywords
methyl
pyrazolone
phenyl
phosphoric acid
dimethyl
Prior art date
Application number
Other languages
German (de)
Inventor
Ag J R Geigy
Original Assignee
Ag J R Geigy
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
Application filed by Ag J R Geigy filed Critical Ag J R Geigy
Publication of CH294598A publication Critical patent/CH294598A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
    • C07J63/006—Expansion of ring C by one atom, e.g. C homo steroids
    • 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
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings
    • 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
    • C07F9/547—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
    • C07F9/6503—Five-membered rings
    • C07F9/65031—Five-membered rings having the nitrogen atoms in the positions 1 and 2
    • 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
    • C07F9/547—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
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/653—Five-membered rings
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6539—Five-membered rings
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
    • C07J63/004—Expansion of ring B by one atom, e.g. B homo steroids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

  

  



  Verfahren zur Herstellung eines Phosphorsäureesters.



  Phosphorsäureester der allgemeinen Formel
EMI1.1     
 worin   R-Y-den    Rest der Enolform R-X-H einer gegebenenfalls substituierten,   nicht-konden-       sierten    heterocyclischen Verbindung mit endocyclischer, enolisierbarer Keto-oder    Thioketogruppe,      Ri    und   X2      Alkyl-,      Alkenyl-,      Alkoxyalkyl-,   
Alkylmercaptoalkyl-oder Halogenalkylreste und   X1      2    und X3 Sauerstoff oder Schwefel   hedeuten,    sind bisher nieht beka. nntgeworden.



   Wie gefunden wurde, besitzen derartige Verbindungen eine sehr gute insektizide und akarizide Wirksamkeit und eignen sich ausgezeichnet als Wirksubstanzen zur Herstellung von SchÏdlingsbckÏmpfungsmitteln, insbesondere zur   Bekämpfung von Aphiden und Acari-    den. Die neuen Verbindungen können sowohl als   Kontaktgifte      als auch intraplantär wirk-    sam sein.



   Viele der erfindungsgemässen Verbindungen besitzen   Anticholinesterase-Wirksamkeit    und eignen sich daher teilweise auch zur Herstellung von Arzneimitteln.



   Man kann die neuen Verbindungen lierstel. len, indem man ein aliphatisehes Phosphorsäure-diester-halogenid bzw. Thiophosphorsäure-diesterhalogenid der allgemeinen Formel
EMI1.2     
 worin Hal Chlor oder Brom bedeutet und Xl, X2 und X3,   RI    und R2 die oben gegebene Be  deutung    haben, mit einer gegebenenfalls substituierten,   nicht-kondensierten      heterocyeli-    schen Verbindung mit endocyclischer enolisierbarer Keto-oder Thioketogruppe, oder mit einem Salz der Enolform einer solchen Verbindung umsetzt.



   Die Umsetzungen k¯nnen in An- oder Ab  wesenheit    von inerten Lösungsmitteln wie Benzol, Toluol, Dioxan, EssigsÏureÏthylester vorgenommen werden. Bei Verwendung der freien heterocyclischen Verbindungen werden mit Vorteil säurebindende Mittel zugesetzt, wie z. B. Natrium-oder Kalium. carbonat. Als Salze der Enole eignen sich insbesondere die Alkalisalze, ferner z. B. auch Salze einwertiger Schwermetalle.



   Zur Herstellung von   Thiophosphorsäure-    estern kann man aber auch zunächst in analoger Weise ein aliphatisehes   Phosphorigsäure-    diesterhalogenid der allgemeinen Formel   
Xi-R,
Hal-P
XoR2    worin Hal,   Xl,      X2,      Ri    und R2 die oben ge  gebene      Bedeuttmg    haben, mit einer   gegebenen-    falls substituierten,   nicht-kondensierten    hetero  cyclischen    Verbindung mit endocyclischer,

   enolisierbarer   Keto-oder Thioketogruppe oder    mit einem Salz der Enolform einer solchen Verbindung umsetzen und den so erhaltenen    heterocyclisch-aliphatischen Phosphorigsällre-    ester der allgemeinen Formel
EMI2.1     
 mit Schwefel oder einer Schwefel abgebenden Verbindung behandeln. Die Schwefelung kann in An-oder Abwesenheit von hochsiedenden Lösungsmitteln, wie o-Dichlorbenzol, Trichlorbenzol, Polybrombenzolen,   a-und      ss-Chlor-    naphthalin bei Temperaturen von etwa 160 bis   200     vorgenommen werden, wobei Katalysatoren, wie   Natriumpolysulfide    oder Phosphor  pentasulfid,    zugesetzt werden können.



   Ferner ist es auch möglich, aber weniger vorteilhaft, die heterocyclische Verbindung vor der oder den aliphatischen Verbindungen mit einem Phosphorsäurehalogenid oder Thiophosphorsäurehalogenid umzusetzen, indem man beispielsweise Phosphoroxyehlorid mit einem Mol der Natriumverbindung eines heterocyclischen   Enols umsetzt    und das so erhaltene Phosphorsäuremonoester-dichlorid z. B. mit 2 Mol Äthylalkohol bzw.   Natriumalkoholat    reagieren lässt.



   Schliesslich kann man zur   Herstelhmg    von heterocyelischen Thiophosphorsäure-S-estern auch ein heterocyclisches   Sulfenylhalogenid    der allgemeinen Formel    RSHal    mit einem aliphatisehen   Phosphorigsäure-    diester der allgemeinen Formel
EMI2.2     
 worin R, Hal, R1 und R2 die oben gegebene Bedeutung haben, umsetzen, wobei unter Abspaltung von Halogenwasserstoff Verbindungen der allgemeinen Formel
EMI2.3     
 entstehen.



   Mit Vorteil wird die Umsetzung in Ge  genwart    eines inerten   Losungsmittels    vorgenommen. Als solche kommen z. B. Kohlenwasserstoffe und Chlorkohlenwasserstoffe, wie Pe  troläther,    Benzol, Chlorbenzol,   Tetrachlorkoh-      lenstoff,    in Frage. Die Reaktion kann durch gelindes Erwärmen und Zusatz von säurebindenden Mitteln, wie   z.    B. Pyridin oder Dimethylanilin, beschleunigt werden.



   Im folgenden sei eine Anzahl in   Betraclil      kommender    heteroeycliseher   Verbinclungen    in Keto-oder   Enolbezeiehnung    aufgezählt : Dioxotetrahydrofuranderivate. wie
3-Methyl-, 3-¯thyl-, 3-Isopropyl- und    3-Isoamyl-2, 4-dioxotetrahydrofuran :      Pyrazolone,    wie z. B.



      Pyrazolon- (5), 3-Methyl-pyrazolon- (5),       1-Methyl-pyrazolon-    (5),    l-Athyl-pyrazolon-    (5).



     1,    3-Dimethyl-pyrazolon-(5).



      1 thyl-3-methyl-pyrazolon- (5),       l-Isopropyl-3-methylpyrazolon-    (5), l-Isoamyl-3-methyl-pyrazolon- (5),    l-Cyclohexyl-3-methyl-pyrazolon-    (5),
3,4-Dimethyl-pyrazolon- (5),    1,    4-DiÏthyl-3-methyl-pyrazolon-(5),    1-Phenyl-pyrazolon-    (5),    l-Phenyl-3-methyl-pyrazolon- (5).   



   1-   (m-Chlor-phenyl)-3-methyl-pyrazolon-      (5),       1-      (p-Nitro-phenyl)-3-methvl-pyrazolon-    (5),   
1- (p-Methoxy-phenyl)-3-methyl-pyrazolon-    l-Phenyl-4-äthyl-pyrazolon- (5), l-Phenyl-3-äthyl-4-methyl-pyrazolon- (5),    l-Phenyl-3-methyl-4-isopropyl-pyrazolon- (5), l-Phenyl-3-methyl-4-benzyl-pyrazolon- (5).       l-Benzyl-3-methyl-pyrazolon-    (5), 
1-(2'-Pyridyl)-3-methyl-pyrazolon-(5),
1-¯thyl-pyrazolon- (3),
1,5-Dimethyl-pyrazolon- (3),    1 thyl-5-methyl-pyrazolon- (3),       1-Phenyl-pyrazolon-    (3), l-Phenyl-5-methyl-pyrazolon- (3),
1-Phenyl-4-methyl-pyrazolon- (3),
1-Phenyl-4, 5-dimethyl-pyrazolon- (3),

     
I-Phenyl-4-cyclohexyl-5-methyl-pyrazolon-     (3),
1-Phenyl-4-benzyl-5-methyl-pyrazolon-(3),   
1-Phenyl-3-methyl-4-chlor-pyrazolon- (5),
I-Phenyl-3-methyl-4-nitro-pyrazolon- (5),
1-Pheny]-3-carbathoxy-pyrazolon- ;      3,    5-Diketo-pyrazolidine, wie l-Methyl-3, 5-diketo-pyrazolidin,
1-Phenyl-3,5-diketo-pyrazolidin,    1,    2-Diphenyl-3, 5-diketo-pyrazolidin,
1,2-Diphenyl-4-butyl-3,5-diketo-pyrazolidin:   3-Methyl-isoxazolon-    (5),
3-Phenyl-isoxazolon- (5) ;    Imidazolon- (2) ; 1-Pheyl-imidazol on- (2).   



     2-Methyl-imidazolon-    ;   4-Methyl-2-oxy-thiazol,       4-Phenyl-2-oxy-thiazol    ; Triazolone, wie z. B.



     I-Phenyl-5-oxy-1,    2,3-triazol,
1-Phenyl-5-methyl-1, 2,4-triazolon-   (3),   
1-Phenyl-5-propyl-1, 2,4-triazolon- (3),
3-Methyl-1, 2,4-triazolon- (5),
1-¯thyl-3-methyl-1, 2,4-triazolon- (5),
3-¯thyl-1, 2, 4-triazolon-(5),    3-Isobutyl-1, 2, 4-triazolon- (5),   
1-Phenyl-1, 2,4-triazolon-   ;    3-Phenyl-1,   2,      4-oxdiazolon-      (5)    ; 3-Methyl-pyron- (2)-on-   (4),       2-Methyl-3-oxy-γ-pyron:    4,   6-I) imethyl-pyridon- (2),   
2,6-Dimethyl-4-oxy-pyridin: 3-Methyl-pyridazon: 2.   4-Dimethyl-6-oxy-pyrimidin,   
2-Propyl-4-methyl-6-oxy-pyrimidin ; 5,6-Diphenyl-3-oxy-1,2,4-triazin:

     2-Methyl-5-oxy-1,    3,4-oxdiazin ; 4-Methyl-2-mercaptothiazol,
1-Methyl-2-mercaptotriazol- ; 1-Phenyl-3-methyl-pyrazol-thion- (5) ; Imidazol-thion- (2),    l-Phenyl-imidazol-thion- ; α-Pyridylmercaptan,  γ-Pyridylmercaptan,   
2,6-Lutidyl-4-mercaptan.



   Neben den vorstehend aufgezählten Verbindungen kommen auch entsprechende Verbindungen in Betracht, welche in den den beterocyclischen Ring   substituierenden    Alkyl Aralkyl-und insbesondere Aryl-Resten ein oder mehrere Halogenatome, Nitrogruppen, Alkoxygruppen oder   Alkylmereaptogruppen,    halogenierte Methylgruppen wie die Trifluormethylgruppe,   Aryloxy-und    Arylmercaptogruppen, substituierte oder acylierte Aminogruppen, Alkyl- und Arylsulfoxyd- und -sul  fongruppen,    halogenierte Alkylsulfongruppen, wie die   Chlormethylsulfongruppe    oder die Trifluormethylsulfongruppe, funktionelle Derivate von Carboxylgruppen wie z. B.

   Carbalkoxy-,   Carbamino-oder      Cyangruppen    ;   Rho-      dangruppen    oder Sulfonamidgruppen enthalten ; die   Aralkyl-und    Arylreste können auch niedrige Alkylgruppen enthalten.



   Als   Phosphorsäure-di-ester-halogenide    der allgemeinen Formel
EMI3.1     
 kommen insbesondere von niedrigen Alkanolen, Alkoxyalkanolen, Halogenalkanolen und entspreehenden Mercaptanen sich ableitende Verbindungen in Frage. Als Alkohole bzw.



  Mercaptane seien beispielsweise genannt : Me  thanol, Äthanol,    n-Propanol, Isopropanol, Allylalkohol, Butylalkohole und Amylalkohole, n-Hexanol, MethoxyÏthanol, ¯thoxyÏthanol, Methylmercapto-Ïthanol, ButoxyÏthanol, 2 Chlor-Ïthanol, 2-Flnor-Ïthanol, 2,3-Dichlorpropanol,   Methyl-,    ¯thyl-, n-Propyl-, Isopropyl-mereaptan, Butyl-und Amylmercaptane,   Methoxyäthyl-mereaptan,    Methylmer   capto-äthyl-mercaptan, 2-Chlor-äthylmercap-    tan.



   Die Phosphorsäure-diester-halogenide sind teilweise bekannt, die bisher nicht   bekannt-    gewordenen lassen sich in analoger Weise, z. B. durch Umsetzung von Phosphoroxyhalogeniden oder   Phosphor-thiohalogeniden    mit 2 Mol von entsprechenden Alkoholen oder Mcrcaptanen bzw. deren Metallverbindungen oder zum Teil auch   dureh    Schwefelung von entsprechenden Phosphorigsäure-diester-halogeniden herstellen.



   Als einzelne Phosphorsäure-diester-halogenide seien genannt : PhosphorsÏure- oder Thiophosphorsäure  -dimethylester-chlorid,  -diÏthylester-chlorid,  -diÏthylester-bromid,     -dipropylester-chlorid, -diisopropylester-chlorid,     -di-amylester-chlorid,  -diallylester-chlorid,  -methyl-allylester-chlorid,  -di-methoxyäthylester-chlorid,    -methyl-chloräthylester-chlorid,     -di-chlorÏthylester-chlorid; ThiophosphorsÏure-O,S-diÏthyl-ester-chlorid, Dithiophosphorsäure-S, S-diäthylester-chlorid, DithiophosphorsÏure-O, S-diäthylester-chlorid,   Dithiophosphorsäure-S,    S-dichloräthylester   ehlorid, Trithiophosphorsäure-dimethylester-chlorid,     -diÏthylester-chlorid.



   Gegenstand vorliegenden Patentes ist nun ein Verfahren zur Herstellung eines Phosphor  säureesters.    Das Verfahren ist dadurch gekennzeichnet, dass man ein Thiophosphorsäureester-halogenid der Formel
EMI4.1     
 worin X Chlor oder Brom bedeutet, mit einer Verbindung der Formel
EMI4.2     
 worin Y einen im Verlaufe des Verfahrens sich abspaltenden Rest, wie Wasserstoff oder ein Kation, bedeutet, umsetzt.



   Die erhaltene neue Verbindung, der Thiophosphorsäure- [2,4-dimethyl-pyrimidyl-   (6)]-    diäthylester, stellt eine leicht gefärbte Flüssigkeit dar, die sich nieht unzersetzt destillieren lässt. Sie soll als Wirksubstanz für Schädlingsbekämpfungsmittel Verwendung finden.



   Betsptel :
124 Teile 2, 4-Dimethyl-6-oxypyrimidin werden mit 138 Teilen Kaliumcarbonat und 2000 Teilen Benzol versetzt und unter Rühren zum Sieden erhitzt. Dabei wird das bei der   Enolathildmg    freiwerdende Wasser mit Benzol azeotrop abdestilliert. Sobald sich im Destillat kein Wasser mehr abseheidet, wird auf 60 bis   70     abgekühlt, 190 Teile Diäthylthio  phosphorsäurechlorid    zugetropft und anschlie¯end 10 Stunden unter Rückfluss gekocht. Nach dem Erkalten wird der Reaktionsmisehung unter gutem Rühren so lange Kaliumearbonatlosung zugesetzt, bis die wässrige Schicht Phenolphthaleinpapier eben rot anfärbt. Nach Abtrennen der wässrigen Sehicht wird das Lösungsmittel abdestilliert.

   Es bleibt der   Thiophosphorsäure-    [2,   4-dimethyl-pyr-       imidyl- (6)]-di-äthylester als schwach gefärbte    Flüssigkeit   zurück,    die sich nicht unzersetzt destillieren lässt. Sie eignet sich ohne weitere Reinigung als Wirkstoff insektizid und akarizid wirksamer Präparate.



  



  Process for producing a phosphoric acid ester.



  Phosphoric acid esters of the general formula
EMI1.1
 wherein R-Y- is the remainder of the enol form R-X-H of an optionally substituted, non-condensed heterocyclic compound with endocyclic, enolizable keto or thioketo group, Ri and X2 are alkyl, alkenyl, alkoxyalkyl,
Alkylmercaptoalkyl or haloalkyl radicals and X1 2 and X3 mean oxygen or sulfur have not yet been known. gotten to.



   As has been found, such compounds have a very good insecticidal and acaricidal activity and are outstandingly suitable as active substances for the production of pest control agents, in particular for combating aphids and acarids. The new compounds can act as contact poisons as well as intraplantar.



   Many of the compounds according to the invention have anticholinesterase activity and are therefore partly also suitable for the production of pharmaceuticals.



   You can erase the new connections. len by adding an aliphatic phosphoric acid diester halide or thiophosphoric acid diester halide of the general formula
EMI1.2
 where Hal is chlorine or bromine and X1, X2 and X3, RI and R2 have the meaning given above, with an optionally substituted, non-condensed heterocyclic compound with an endocyclic enolizable keto or thioketo group, or with a salt of the enol form such a connection.



   The reactions can be carried out in the presence or absence of inert solvents such as benzene, toluene, dioxane, ethyl acetate. When using the free heterocyclic compounds acid-binding agents are added with advantage, such as. B. sodium or potassium. carbonate. Particularly suitable salts of the enols are the alkali metal salts, also, for. B. also salts of monovalent heavy metals.



   To prepare thiophosphoric acid esters, however, an aliphatic phosphorous acid diester halide of the general formula can also initially be prepared in an analogous manner
Xi-R,
Hal-P
XoR2 where Hal, Xl, X2, Ri and R2 have the meaning given above, with an optionally substituted, non-condensed heterocyclic compound with endocyclic,

   Reacting enolizable keto or thioketo group or with a salt of the enol form of such a compound and the heterocyclic-aliphatic phosphorous acid residue of the general formula obtained in this way
EMI2.1
 treat with sulfur or a sulfur-releasing compound. The sulphurisation can be carried out in the presence or absence of high-boiling solvents such as o-dichlorobenzene, trichlorobenzene, polybromobenzenes, α- and β-chloronaphthalene at temperatures of about 160 to 200, with catalysts such as sodium polysulphides or phosphorus pentasulphide being added can.



   Furthermore, it is also possible, but less advantageous, to implement the heterocyclic compound before the aliphatic compound or compounds with a phosphoric acid halide or thiophosphoric acid halide, for example by reacting phosphorus oxychloride with one mole of the sodium compound of a heterocyclic enol and the phosphoric acid monoester dichloride obtained in this way e.g. B. can react with 2 moles of ethyl alcohol or sodium alcoholate.



   Finally, for the production of heterocyclic thiophosphoric acid S-esters, a heterocyclic sulfenyl halide of the general formula RSHal with an aliphatic phosphorous acid diester of the general formula can also be used
EMI2.2
 in which R, Hal, R1 and R2 have the meaning given above, react, with elimination of hydrogen halide compounds of the general formula
EMI2.3
 arise.



   The reaction is advantageously carried out in the presence of an inert solvent. As such come z. B. hydrocarbons and chlorinated hydrocarbons, such as petroleum ether, benzene, chlorobenzene, carbon tetrachloride, in question. The reaction can be initiated by gentle heating and the addition of acid-binding agents, such as. B. pyridine or dimethylaniline are accelerated.



   A number of heteroeyclic compounds in keto or enol denominations are listed below: Dioxotetrahydrofuran derivatives. how
3-methyl-, 3-¯thyl-, 3-isopropyl- and 3-isoamyl-2, 4-dioxotetrahydrofuran: pyrazolones, such as. B.



      Pyrazolone- (5), 3-methyl-pyrazolone- (5), 1-methyl-pyrazolone- (5), 1-ethyl-pyrazolone- (5).



     1,3-Dimethyl-pyrazolone- (5).



      1-ethyl-3-methyl-pyrazolone- (5), l-isopropyl-3-methylpyrazolone- (5), l-isoamyl-3-methyl-pyrazolone- (5), l-cyclohexyl-3-methyl-pyrazolone- ( 5),
3,4-dimethyl-pyrazolone- (5), 1,4-diethyl-3-methyl-pyrazolone- (5), 1-phenyl-pyrazolone- (5), l-phenyl-3-methyl-pyrazolone- (5 ).



   1- (m-chloro-phenyl) -3-methyl-pyrazolone- (5), 1- (p-nitro-phenyl) -3-methvl-pyrazolone- (5),
1- (p-methoxyphenyl) -3-methyl-pyrazolone- l-phenyl-4-ethyl-pyrazolone- (5), l-phenyl-3-ethyl-4-methyl-pyrazolone- (5), l- Phenyl-3-methyl-4-isopropyl-pyrazolone- (5), 1-phenyl-3-methyl-4-benzyl-pyrazolone- (5). l-benzyl-3-methyl-pyrazolone- (5),
1- (2'-pyridyl) -3-methyl-pyrazolone- (5),
1-ethyl-pyrazolon- (3),
1,5-dimethyl-pyrazolone- (3), 1-thyl-5-methyl-pyrazolone- (3), 1-phenyl-pyrazolone- (3), 1-phenyl-5-methyl-pyrazolone- (3),
1-phenyl-4-methyl-pyrazolone- (3),
1-phenyl-4,5-dimethyl-pyrazolon- (3),

     
I-phenyl-4-cyclohexyl-5-methyl-pyrazolone- (3),
1-phenyl-4-benzyl-5-methyl-pyrazolone- (3),
1-phenyl-3-methyl-4-chloro-pyrazolone- (5),
I-phenyl-3-methyl-4-nitro-pyrazolone- (5),
1-pheny] -3-carbathoxy-pyrazolone-; 3, 5-diketo-pyrazolidines, such as l-methyl-3, 5-diketo-pyrazolidine,
1-phenyl-3,5-diketo-pyrazolidine, 1,2-diphenyl-3, 5-diketo-pyrazolidine,
1,2-diphenyl-4-butyl-3,5-diketo-pyrazolidine: 3-methyl-isoxazolone- (5),
3-phenyl-isoxazolone- (5); Imidazolone- (2); 1-Pheyl-imidazol-one- (2).



     2-methyl-imidazolone-; 4-methyl-2-oxy-thiazole, 4-phenyl-2-oxy-thiazole; Triazolones, such as B.



     I-phenyl-5-oxy-1, 2,3-triazole,
1-phenyl-5-methyl-1, 2,4-triazolon- (3),
1-phenyl-5-propyl-1, 2,4-triazolon- (3),
3-methyl-1,2,4-triazolon- (5),
1-ethyl-3-methyl-1,2,4-triazolon- (5),
3-¯thyl-1, 2, 4-triazolon- (5), 3-isobutyl-1, 2, 4-triazolon- (5),
1-phenyl-1,2,4-triazolone-; 3-phenyl-1, 2, 4-oxdiazolon- (5); 3-methyl-pyrone- (2) -one- (4), 2-methyl-3-oxy- γ-pyrone: 4, 6-I) imethyl-pyridon- (2),
2,6-dimethyl-4-oxy-pyridine: 3-methyl-pyridazon: 2.4-dimethyl-6-oxy-pyrimidine,
2-propyl-4-methyl-6-oxy-pyrimidine; 5,6-Diphenyl-3-oxy-1,2,4-triazine:

     2-methyl-5-oxy-1,3,4-oxdiazine; 4-methyl-2-mercaptothiazole,
1-methyl-2-mercaptotriazole-; 1-phenyl-3-methyl-pyrazol-thione- (5); Imidazol-thione- (2), l-phenyl-imidazol-thione-; α-pyridyl mercaptan, γ-pyridyl mercaptan,
2,6-lutidyl-4-mercaptan.



   In addition to the compounds listed above, suitable compounds are also suitable which substituted one or more halogen atoms, nitro groups, alkoxy groups or alkylmereapto groups, halogenated methyl groups such as the trifluoromethyl group, aryloxy and aryl mercapto groups in the alkyl aralkyl and in particular aryl radicals that substitute for the beterocyclic ring or acylated amino groups, alkyl and arylsulfoxyd and sulfonic groups, halogenated alkylsulfone groups, such as the chloromethylsulfone group or the trifluoromethylsulfone group, functional derivatives of carboxyl groups such as. B.

   Carbalkoxy, carbamino or cyano groups; Contain rhodium groups or sulfonamide groups; the aralkyl and aryl radicals can also contain lower alkyl groups.



   As phosphoric acid diester halides of the general formula
EMI3.1
 In particular, compounds derived from lower alkanols, alkoxyalkanols, haloalkanols and corresponding mercaptans are suitable. As alcohols or



  Mercaptans may be mentioned, for example: methanol, ethanol, n-propanol, isopropanol, allyl alcohol, butyl alcohols and amyl alcohols, n-hexanol, methoxyanolthanol, ¯thoxyÏthanol, methylmercaptothanol, butoxyÏthanol, 2-chloroethanol, 2-flnorethanol, 2, 3-dichloropropanol, methyl, ethyl, n-propyl, isopropyl mereaptane, butyl and amyl mercaptans, methoxyethyl mereaptane, methylmer captoethyl mercaptan, 2-chloroethyl mercaptan.



   Some of the phosphoric acid diester halides are known, but those not previously known can be processed in an analogous manner, e.g. B. by reacting phosphorus oxyhalides or phosphorothiohalides with 2 moles of corresponding alcohols or Mcrcaptanen or their metal compounds or sometimes also by sulfurizing the corresponding phosphorous acid diester halides.



   Individual phosphoric acid diester halides that may be mentioned are: Phosphoric acid or thiophosphoric acid dimethyl ester chloride, diethyl ester chloride, diethyl ester bromide, dipropyl ester chloride, diisopropyl ester chloride, di-amyl ester chloride, diallyl ester chloride , methyl allyl ester chloride, di-methoxyethyl ester chloride, methyl chloroethyl ester chloride, di-chloroethyl ester chloride; Thiophosphoric acid-O, S-diethyl ester chloride, dithiophosphoric acid-S, S-diethyl ester chloride, dithiophosphoric acid-O, S-diethyl ester chloride, dithiophosphoric acid-S, S-dichloroethyl ester chloride, trithiophosphoric acid-dimethyl ester chloride.



   The present patent is now a process for the preparation of a phosphoric acid ester. The process is characterized in that a thiophosphoric acid ester halide of the formula
EMI4.1
 wherein X is chlorine or bromine, with a compound of the formula
EMI4.2
 where Y is a radical which is split off in the course of the process, such as hydrogen or a cation.



   The new compound obtained, the thiophosphoric acid [2,4-dimethyl-pyrimidyl- (6)] diethyl ester, is a slightly colored liquid that cannot be distilled undecomposed. It is said to be used as an active ingredient for pesticides.



   Betsptel:
124 parts of 2,4-dimethyl-6-oxypyrimidine are mixed with 138 parts of potassium carbonate and 2000 parts of benzene and heated to the boil with stirring. The water released during enolate formation is azeotropically distilled off with benzene. As soon as no more water separates out in the distillate, the mixture is cooled to 60 to 70, 190 parts of diethylthiophosphoric acid chloride are added dropwise and the mixture is then refluxed for 10 hours. After cooling down, potassium carbonate solution is added to the reaction mixture with thorough stirring until the aqueous layer of phenolphthalein paper just turns red. After the aqueous layer has been separated off, the solvent is distilled off.

   The thiophosphoric acid [2,4-dimethyl-pyrimidyl- (6)] -di-ethyl ester remains as a weakly colored liquid which cannot be distilled without decomposition. It is suitable as an active ingredient in insecticidal and acaricidal preparations without further cleaning.

Claims (1)

PATENTANSPRUCH : Verfahren zur Herstellung eines Phos- phorsäureesters, dadurch gekennzeichnet, dass man ein Thiophosphorsäureesterhalogenid der Formel EMI5.1 vorin X Chlor oder Brom bedeutet, mit einer @erbindung der Formel EMI5.2 worin Y einen im Verlaufe des Verfahrens sich abspaltenden Rest bedeutet, umsetzt. PATENT CLAIM: Process for the preparation of a phosphoric acid ester, characterized in that a thiophosphoric acid ester halide of the formula EMI5.1 vorin X denotes chlorine or bromine, with a compound of the formula EMI5.2 where Y is a radical which is split off in the course of the process. Die erhaltene neue Verbindung, der Thiophosphorsäure- [2,4-dimethyl-pyrimidyl- (6)]diäthylester, stellt eine leieht gefärbte Fliissigkeit dar, die sich nicht unzersetzt destillieren lässt. The new compound obtained, thiophosphoric acid [2,4-dimethyl-pyrimidyl- (6)] diethyl ester, is a slightly colored liquid which cannot be distilled without decomposition. UNTERANSPRUCH : Verfahren naeh Patentanspruch, dadureh gekennzeichnet, dass man ein Alkalisalz des 2,4-Dimethyl-6-oxy-pyrimidins mit Diäthyl- thiophosphorsäurechlorid umsetzt. SUBClaim: Process according to patent claim, characterized in that an alkali salt of 2,4-dimethyl-6-oxy-pyrimidine is reacted with diethyl thiophosphoric acid chloride.
CH294598D 1951-04-20 1951-04-20 Process for producing a phosphoric acid ester. CH294598A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH294598T 1951-04-20

Publications (1)

Publication Number Publication Date
CH294598A true CH294598A (en) 1953-11-30

Family

ID=4488570

Family Applications (3)

Application Number Title Priority Date Filing Date
CH300737D CH300737A (en) 1951-04-20 1951-04-20 Process for producing a phosphoric acid ester.
CH294598D CH294598A (en) 1951-04-20 1951-04-20 Process for producing a phosphoric acid ester.
CH300761D CH300761A (en) 1951-04-20 1951-04-20 Process for producing a phosphoric acid ester.

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CH300737D CH300737A (en) 1951-04-20 1951-04-20 Process for producing a phosphoric acid ester.

Family Applications After (1)

Application Number Title Priority Date Filing Date
CH300761D CH300761A (en) 1951-04-20 1951-04-20 Process for producing a phosphoric acid ester.

Country Status (1)

Country Link
CH (3) CH300737A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4531005A (en) * 1981-02-04 1985-07-23 Takeda Chemical Industries, Ltd. Pyrazol-4-yl phosphites

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4531005A (en) * 1981-02-04 1985-07-23 Takeda Chemical Industries, Ltd. Pyrazol-4-yl phosphites

Also Published As

Publication number Publication date
CH300761A (en) 1954-08-15
CH300737A (en) 1954-08-15

Similar Documents

Publication Publication Date Title
DE910652C (en) Process for the production of phosphoric acid esters
DE864252C (en) Process for the production of phosphoric acid esters
US2908605A (en) New organic phosphorus compounds and process for their manufacture
US3019250A (en) Thiophosphoric acid esters and a process for their production
US2959516A (en) Organic phosphate compounds and use thereof
DE1150387B (en) Process for the production of di- or trithiophosphonic acid esters
DE1134372B (en) Process for the production of phosphine or. Thionophosphinic acid esters
DE1170400B (en) Process for the preparation of (thio) -phosphorus (phosphonic, -phosphine) acid esters
CH294598A (en) Process for producing a phosphoric acid ester.
DE956503C (en) Process for the production of new phosphoric or thiophosphoric acid esters
DE2200467A1 (en) New esters
EP0053787B1 (en) S-bromo derivatives of dithiophosphoric acid, dithiophosphonic acid and dithiophosphinic acid and process for their preparation
DE1139492B (en) Process for the production of dithiolphosphonic acid esters
DE961083C (en) Process for the preparation of S-ª ‰ -Merkapto-aethyl-O, O-dialkyl-thiol-phosphoric acid esters
DE1167831B (en) Process for the preparation of tertiary diarylalkyl or diaryl aralkylphosphine oxides
EP0207412B1 (en) Process for preparing esters of (thiono)phosphoric acid
DE1963672A1 (en) Dithiophosphoric acid esters, their production and use as pest control agents
US3031488A (en) New compounds of omiron, omiron'-dialkylthiophosphoric acids and a process for their production
EP0033827A1 (en) Preparation of fluorsulfonyl benzyl phosphonic acid esters and new fluorsulfonyl benzyl phosphonic acid esters
DE1139493B (en) Process for the preparation of thionothiolphosphonic acid esters
US2884438A (en) O-cyclohexylphenyl o,o-dialkyl phosphorothioates
DE3203538A1 (en) 4-PYRAZOLYLPHOSPHITE AND METHOD FOR THE PRODUCTION THEREOF
DE1167845B (en) Process for the production of phosphoric acid, phosphonic acid and phosphinic acid esters or the corresponding thiono-esters of 5-oxypiazthiol
DE1795350C3 (en) Pyrimldinylthiophosphoric acid esters, process for their preparation and compositions containing them
DE1198350B (en) Process for the production of dialkylenol phosphates of alpha-alkoxalyl lactones which are effective as pest control agents