CH516595A - New insecticidal phosphoric esters - Google Patents

New insecticidal phosphoric esters

Info

Publication number
CH516595A
CH516595A CH1255369A CH1255369A CH516595A CH 516595 A CH516595 A CH 516595A CH 1255369 A CH1255369 A CH 1255369A CH 1255369 A CH1255369 A CH 1255369A CH 516595 A CH516595 A CH 516595A
Authority
CH
Switzerland
Prior art keywords
sep
formula
dest
hal
alkyl
Prior art date
Application number
CH1255369A
Other languages
German (de)
Inventor
Henry Dr Martin
Jozef Dr Drabek
Original Assignee
Ciba Geigy 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 BE754922D priority Critical patent/BE754922A/en
Application filed by Ciba Geigy Ag filed Critical Ciba Geigy Ag
Priority to CH1255369A priority patent/CH516595A/en
Priority to CH1490871A priority patent/CH528865A/en
Priority to DE19702039529 priority patent/DE2039529A1/en
Priority to FR7029560A priority patent/FR2056852A5/fr
Priority to IL35116A priority patent/IL35116A0/en
Priority to US00064648A priority patent/US3732343A/en
Priority to NL7012129A priority patent/NL7012129A/xx
Priority to ZA705638A priority patent/ZA705638B/en
Priority to ES382810A priority patent/ES382810A1/en
Priority to GB3975370A priority patent/GB1321087A/en
Publication of CH516595A publication Critical patent/CH516595A/en
Priority to US00332470A priority patent/US3852438A/en
Priority to US00332469A priority patent/US3840660A/en

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Classifications

    • 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
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • 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
    • 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
    • C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols

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

Abstract

New insecticidal phosphoric esters. Cpds. are of formula R1OP(O)(OR2)-O-C(CH2-Hal)-OR3 where hal is Cl or Br; R1 and R2 are same or diff. 1-4C alkyl, R3 is aryl esp. phenyl or naphthyl, opt. substd. by halogen-1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, 1-4C alkylsulphinyl, 1-4C alkylsulphonyl, NO2, CF3, CN,SCN, COO (1-4C alkyl) or -CO(1-4C alkyl). Prepd. by reacting (hal)2CHCOOR3 with R1O-P(OR2)-OR4where R4 is 1-4C alkyl. Esp. effective against insects, nematodes, Acarids, bateria, and phytopathogenic fungi.

Description

  

  
 



  Verfahren zur   Herstellung    neuer   Phosphorsäureester   
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer Phosphorsäureester der Formel
EMI1.1     
 worin Hal Chlor oder Brom bedeutet,   Rt    und R2 gleich oder verschieden sind und   C-C4-Alkylreste    bedeuten und R3 ein gegebenenfalls durch Halogen,   C1-C4    Alkyl,   C-C4    Alkoxy,   C3-C4    Alkylthio,   C,-C4    Alkylsulfinyl-,   C1-C4Alkylsullonyl,    -NO2, -CF3, -CN, -SCN,    -NOs      -CFs    -CN   -SCN   
EMI1.2     
   -COOAlkyi(C1-C4)    oder -COOAryl substituiertes Aryl-, insbesondere Phenylradikal darstellt, dadurch gekennzeichnet,

   dass man einen Dihalogenessigsäureester der Formel    (Hal)2CH-COOR3    worin Hal Chlor oder Brom bedeutet und R3 die für Formel I gegebene Definition zukommt, mit einem Trialkylphosphit der Formel
EMI1.3     
 umsetzt, worin   Rt    und R2 die erwähnte Bedeutung haben und R4 einen   C-C4-Alkylrest    darstellt. Die Reaktion kann in einem Lösungsmittel wie Toluol, Xylol, Petroläther, Dioxan vorgenommen werden, abhängig von der Schnelligkeit oder Trägheit der   jewéí-    ligen Umsetzung.



   Diese Reaktion ist überraschend, denn in der Literatur (F. W. Lichtenthaler, Chem. Rev. 61, 612 [1961]) wird zur Erläuterung der Perkow-Reaktion ausdrücklich ausgeführt, dass die Umsetzung von Tri äthylphosphit mit Dichloressigsäureäthylester nur   un-    definierte Endprodukte neben   C2HsCl    ergibt. Dichloressigsäureester, so wird gesagt, eignen sich nicht für die   Perkow-Reaktion   
Unter Halogen als Substituent des Arylrestes   R3    werden Fluor, Chlor, Brom und Jod verstanden.



   Besonders geeignete Wirkstoffe sind diejenigen der Formel I, worin Hal Chlor oder Brom bedeutet, R1 und R2 Methyl oder Äthyl darstellen und R3 eine gegebenenfalls durch einen oder mehrere der Substituenten Halogen, Methyl,   22ithyle    Methoxy,   Äthoxy,    Methylmercapto, Methylsulfinyl, Methylsulfonyl, -NO2,   -CF3,    -CN,   -SCN,    Carbäthoxy, Carbomethoxy, substituierte Phenylgruppe bedeuten.



   Von diesen haben solche Verbindungen eine besonders gute Wirkung, worin Hal Chlor ist und der Substituent R3 eine durch einen oder mehrere der Substituenten Chlor, Brom, Jod, -CN,   -NOe    oder -CF3 substitu   vierte    Phenylgruppe bedeutet, die ausserdem noch Methyl oder Äthyl enthalten kann.  



   Die neuen Phosphorsäureester der Formel I wirken beispielsweise gegen Insekten, Nematoden und Vertreter der Ordnung Acarina sowie gegen pflanzenpathogene Bakterien und Pilze. In entsprechend höheren Aufwandmengen zeigen sie auch eine herbizide und entblätternde Wirkung.



   Ihr Hauptanwendungsgebiet ist die Bekämpfung aller Entwicklungsstadien von saugenden und beissenden Insekten und Acarina, d. h. von Eiern, Larven, Puppen, Nymphen und Adulten bzw. Imagines.



   Zu den saugenden Insekten gehören Dipteren und Hymenopteren, z. B. Blattläuse (Aphidae) wie Myzus persicae, Doralis fabae, Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solanifolii, Cryptomyzus korschelti, Sappaphis mali, Hyalopterus arundinis, Myzus cerasi, dann Schild- und Wolläuse (Coccina), z. B.



  Aspidiotus hederae, Lecanium hesperidum, Pseudococcus maritimus, Thripsarten (Thysanoptera) z. B. Hercinothrips femoralis, Wanzen z. B. Piesma quadrata, Rhodnius prolixus, Triatoma infestans, Zikaden z. B.



  Euscelis bilobatus oder Nephotettix bipunctatus.



   Unter den beissenden Insekten sollen die Lepidopteren und Coleopteren erwähnt werden z. B. Plutella maculipennis, Lymantria dispar, Euproctis chrysorrhoea, Malocosoma neustria, Mamestra brassicae, Agrotis segetum, Pieris brassicae, ferner Prodenia litura, Ephestia kühniella, Galleria mellonella, dann Schädlinge der Vorratshaltung wie Dermestes frischii, Trogoderma granarius, Tribolium castaneum, Calandra und Sitophilus zea mais, Stegobium paniceum, Tenebrio molitor, Oryzaephilus surinamensis, Blattela germanica, Periplaneta americana, Blatta orientalis, Blaberus gigantus, Blaberus fuscus, Gryllus domesticus, Sitophilus granarius, Leptinotarsa decemlineata; im Boden lebende Arten wie Agriotes sp., Melolontha melolontha; Termiten wie Leucotermes reticulitermes sp.



  oder Leucotermes flavipes.



   Eine grössere Anzahl Schädlinge ist unter der Ordnung Acarina zu finden, z. B. Milben und davon besonders Spinnmilben (Tetranychidae) wie Tetranychus telarius, T. althaeae, T. urticae, Paratetranychus pilosus, Panonychus ulmi, dann Gallmilben (Eriophyes ribis) und Tarsonemiden wie Hemitarsonemus latus oder Tarsonemus pallidus.



   Unter die Ordnung Acarina fallen aber auch die Zecken, d. h. Ektoparasiten wie Boophilus microplus Dermanyssus gallinae, Ornithonyssus bacoti, Ornithonyssus sylviarum, Rhipicephalus bursa, Pneumonyssus caninum, Laelaps nutalli, Acarapis woodi, Psorergates ovis.



   Diese Zusammenstellung von Schädlingen erhebt keinerlei Anspruch auf Vollständigkeit. Grundsätzlich haben die Phosphate der Formel   I    eine starke Wirkung gegen Insekten und Acarina, die als Schädlinge in Nutzpflanzenkulturen bekannt sind. So wird etwa der Reisstengelbohrer Chilo suppressalis bereits mit Wirkstoffmengen von   0,02 /o    vollständig abgetötet.



   Die Wirkstoffe der Formel I zeigen ausser der insektiziden und akariziden Wirkung auch eine starke Wirkung gegen pflanzenpathogene Nematoden, von denen folgenden Ordnungen genannt werden sollen:
Aphelenchoides, z. B. Aphelenchus ritzemabosi, Aphelenchus fragariae, Aphelenchus oryzae, dann Ditylenchoides z. B. Ditylenchus dipsaci, ferner Meloidogyne, z. B. Meloidogyne arenaria, Meloidogyne incognita, dann zystenbildende Nematoden (Heterodera), z. B. Heterodera rostochiensis, Heterodera schachtii, dann Wurzelnematoden wie Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema, Rhadopholus.



   Beispiel 1
Herstellung von   0,0-Diäthyl-1-(4-    chlorphenoxy)-2-chlor-vinylphosphat
EMI2.1     

47,6 g   Dichloressigsäure-4-Chlorphenylester    wurden in 100 ml Toluol gelöst. In diese Lösung wurden 40 g Triäthylphosphit zugegeben, woraufhin das Reaktionsgemisch auf   110"C    erwärmt und bei dieser Temperatur 16 Stunden gehalten wurde.



   Das Toluol wurde anschliessend abgezogen und das Rohprodukt mittels einer Molekulardestillationsapparatur gereinigt.



   Ausbeute 35,3 g; Kp: 1000 C/0,003 - 0,004 Torr
Analyse für   CX2Ht5C1205P    berechnet: P 9,1   O/o      CI    20,8 O/o gefunden: P 8,9   O/o      CI    21,3   O/o   
Die Struktur des Produktes wurde mittels IR-Analyse bestätigt. Bei Zugabe von   SO2Cl2    in   CH2Cl2    wurde an die Doppelbindung Cl2 addiert. 

  Das gebildete gelbliche Trichloräthylphosphat zeigt folgende Analysenwerte für    Cl2Ht5a405P:    berechnet: P   7,52 /o      Q      34,42 O/o    gefunden: P 7,7   O/o    CI 34,9   O/o    In   ähnlicher    Weise lassen sich die folgenden Phosphorsäureester gewinnen:
EMI2.2     


<tb> Wirkstoff <SEP> Hal <SEP> Rs <SEP> Kp/mmHg
<tb> Nr. <SEP> R1=Rn
<tb> 2 <SEP> C2H5 <SEP> CI <SEP> Cl <SEP> 1000 <SEP> C/0,001
<tb>  <SEP> - <SEP> (Md. <SEP> Dest.)
<tb>  <SEP> Cl
<tb>   
EMI3.1     


<tb> Wirkstoff <SEP> Hal <SEP> R8 <SEP> Kp/mmHg
<tb> Nr. <SEP> R1=R2
<tb> 3 <SEP> CH5 <SEP> C1 <SEP> zuCl <SEP> 1240C/0,005
<tb> 4 <SEP> CH3 <SEP> CZ <SEP> C1 <SEP> 1300 <SEP> C/0,001
<tb>  <SEP> - <SEP> (Mol.

  <SEP> Dest.)
<tb>  <SEP> CF5
<tb> 5 <SEP> CHs <SEP> Cl <SEP> Q¯CFs <SEP> 1300 <SEP> C/0,001
<tb>  <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> C1
<tb> 6 <SEP> CH3 <SEP> CI <SEP> 1¯NOz <SEP> 1350 <SEP> C/0,001
<tb>  <SEP>  <  <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> CH3
<tb> 7 <SEP> CH3 <SEP> Cl <SEP> /NO2 <SEP> 1350 <SEP> C/0,001
<tb>  <SEP>  <  <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> C1
<tb> 8 <SEP> C2H5 <SEP> C1 <SEP> - t <SEP> F¯Cl <SEP> 1350 <SEP> C/0,001
<tb>  <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> CFs
<tb> 9 <SEP> C2H5 <SEP> C1 <SEP> ¯ <SEP> /CFa <SEP> 1350 <SEP> C/O,001
<tb>  <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> C1
<tb> 10 <SEP> C2H5 <SEP> Cl <SEP> /N02 <SEP> 1400 <SEP> C/0,001
<tb>  <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> CH3
<tb> 11 <SEP> H5 <SEP> Q <SEP> -4/ <SEP> r <SEP> O2 <SEP> 1300 <SEP> C/0,001
<tb>  <SEP> - <SEP> (Mol.

  <SEP> Dest.)
<tb>  <SEP> C1
<tb> 12 <SEP> QH5 <SEP> Cl <SEP> zu <SEP> 110  <SEP> C/0,003
<tb>  <SEP> (Moll. <SEP> Dest.)
<tb> 13 <SEP> C2H5 <SEP> C1 <SEP> zu <SEP> 124-1320 <SEP> C/0,06
<tb>  <SEP> Cl
<tb> 14 <SEP> CsH5 <SEP> Cl <SEP> 9 <SEP> 125  <SEP> C/0,008
<tb>  <SEP> Cl
<tb> 15 <SEP> C2H5 <SEP> Cl <SEP> vC1 <SEP> 130  <SEP> C/0,02
<tb>  <SEP> Ci.
<tb>   
EMI4.1     





  Wirkstoff <SEP> Hai <SEP> Ra <SEP> Kp/mmHg
<tb> Wir}stoff <SEP> Hal <SEP> RJ <SEP> Kp/mmHg
<tb> Nr. <SEP> R=R2
<tb> 16 <SEP> CI <SEP> a <SEP> C1 <SEP> 145  <SEP> C/0,03
<tb>  <SEP> ¸
<tb> 17 <SEP> CsH6 <SEP> Q <SEP> ) <SEP> C1 <SEP> 136" <SEP> C/O,001
<tb>  <SEP> C1 <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> CI
<tb> 18 <SEP> CH1 <SEP> CI <SEP> C1 <SEP> Smp.:

  <SEP> 900 <SEP> C
<tb>  <SEP> b
<tb>  <SEP> -5J
<tb> 19 <SEP> c'H1 <SEP> a <SEP> tBr <SEP> 123  <SEP> C/0,001
<tb> 20 <SEP> ctH5 <SEP> Cl <SEP> 135" <SEP> C/( > ,003
<tb>  <SEP> llr
<tb> 21 <SEP> c'H1 <SEP> Cl <SEP> wO¯CI <SEP> 132137" <SEP> C/0,022
<tb>  <SEP> C;
<tb> 22 <SEP> H5 <SEP> CI <SEP> CHa <SEP> 115-118  <SEP> C/0,008
<tb> 23 <SEP> H5 <SEP> CI <SEP> C1 <SEP> nicht <SEP> desilierbar
<tb>  <SEP> CH,
<tb> 24 <SEP> H5 <SEP> CI <SEP> TISCHS <SEP> nicht <SEP> desdllierbar
<tb> 25 <SEP> CHi <SEP> a <SEP> tNO2 <SEP> nicht <SEP> destillierbar
<tb> 26 <SEP> a <SEP> CI <SEP> CF. <SEP> 130  <SEP> C/0,002
<tb>  <SEP> (Mol. <SEP> Det)
<tb> 27 <SEP> H1 <SEP> CI <SEP> 9 <SEP> 1240 <SEP> C10,015
<tb>  <SEP> CHa
<tb> 28 <SEP> C;H5 <SEP> a <SEP> -Ct <SEP> 1300 <SEP> C/0,02
<tb>   
EMI5.1     


<tb> Wirkstoff <SEP> Hal <SEP> Rs <SEP> Kp/mmHg
<tb> Nr.

  <SEP> R,=R2
<tb> 29 <SEP> H5 <SEP> Cl <SEP> 9 <SEP> 145-1520 <SEP> C/0,03
<tb>  <SEP> OCH8
<tb> 30 <SEP> C2H5 <SEP> CL <SEP> 9 <SEP> 137-1450 <SEP> C/0,05
<tb>  <SEP> OCHs
<tb> 31 <SEP> H5 <SEP> CI <SEP> OCH3 <SEP> 1650C/o,02
<tb> 32 <SEP> C2H5 <SEP> CL <SEP> XC1 <SEP> 1420 <SEP> C/0,015
<tb>  <SEP> CH3
<tb> 33 <SEP> H5 <SEP> Cl <SEP> zu <SEP> 1400 <SEP> C/0,001
<tb>  <SEP> (Mol. <SEP> (Md. <SEP> Dest.)
<tb> 34 <SEP> H5 <SEP> a <SEP> 9CI <SEP> 1160 <SEP> C/0,01
<tb>  <SEP> C(CHa)8
<tb> 35 <SEP> C2H5 <SEP> Cl <SEP> COOCH5 <SEP> 1400C/O,02
<tb> 36 <SEP> C2H5 <SEP> Cl <SEP> 9 <SEP> 13514O0 <SEP> C/O,02
<tb>  <SEP> COOCHs
<tb> 37 <SEP> CH3 <SEP> C1 <SEP> oC1 <SEP> 126  <SEP> C/0,02
<tb>  <SEP> CI
<tb> 38 <SEP> CH3 <SEP> C1 <SEP> C1 <SEP> 1500 <SEP> C/0,03
<tb>  <SEP> ¯C1
<tb>  <SEP> C1
<tb> 39 <SEP> CH3 <SEP> Cl <SEP> /Cl <SEP> 1300 <SEP> C/O,001
<tb>  <SEP> - <SEP> (Mol.

  <SEP> Dest.)
<tb>  <SEP> Cl
<tb> 40 <SEP> CH3 <SEP> Cl <SEP> yl <SEP> 122" <SEP> C/0,02
<tb>  <SEP> C1
<tb> 41 <SEP> C2H5 <SEP> Cl <SEP>  < 2 <SEP> 1300 <SEP> C/O,O2
<tb>  <SEP> COOCHs
<tb>   
EMI6.1     


<tb> Wirkstoff <SEP> Hal <SEP> Rs <SEP> Kp/mmHg
<tb> Nr. <SEP> R1=R2
<tb> 42 <SEP> H5 <SEP> Cl <SEP> /CN <SEP> , <SEP> 1400 <SEP> C/0,001
<tb>  <SEP> (Md. <SEP> Dest.)
<tb> 43 <SEP> C2Hs <SEP> Cl <SEP> Cl <SEP> 137  <SEP> C/0,001
<tb>  <SEP> (Mol. <SEP> (Mol. <SEP> C1 <SEP> 1370 <SEP> Dest.)
<tb>  <SEP> (M. <SEP> Dest.)
<tb>  <SEP> Cl
<tb> 44 <SEP> C2H5 <SEP> Cl <SEP> C1 <SEP> Smp.: <SEP> 840 <SEP> C
<tb>  <SEP> C1
<tb> 45 <SEP> H5 <SEP> Cl <SEP> CHs <SEP> 1350 <SEP> C/0,001
<tb>  <SEP> cFC <SEP> C1 <SEP> (Ma <SEP> Des. > 
<tb>  <SEP> C1 <SEP> CHs
<tb> 46 <SEP> H5 <SEP> Cl <SEP> CHs <SEP> 1360 <SEP> C/0,001
<tb>  <SEP> j¸Cl <SEP> (Mol.

  <SEP> Dest.)
<tb>  <SEP> C1
<tb> 47 <SEP> C2H <SEP> C1 <SEP> NO2 <SEP> 1300 <SEP> C/0,001
<tb>  <SEP> \iJ <SEP> (Mo. <SEP> Dest.)
<tb>  <SEP> C1
<tb> 48 <SEP> H5 <SEP> C1 <SEP> /Br <SEP> 1350 <SEP> C/0,005
<tb>  <SEP> r <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> OCHs
<tb> 49 <SEP> C2H5 <SEP> Cl <SEP> Cl <SEP> 135  <SEP> C/0,005
<tb>  <SEP> t <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> Br
<tb> 50 <SEP> H5 <SEP> Ci <SEP> -CoCls <SEP> 1800 <SEP> C/0,08
<tb> 51 <SEP> CH <SEP> Cl <SEP> /CN <SEP> 1250 <SEP> C/O,001
<tb>  <SEP> (Mol. <SEP> Dest.)
<tb> 52 <SEP> H <SEP> Cl <SEP> Br <SEP> 145  <SEP> C/0,005
<tb>  <SEP> ¯Br <SEP> OMoa. <SEP> Dest.)
<tb>  <SEP> OCHs
<tb>  <SEP> OCHs
<tb>   
EMI7.1     


<tb> Wirkstoff <SEP> Hal <SEP> R3 <SEP> Kp/mmHg
<tb> Nr. <SEP> R1=R2
<tb> 53 <SEP> H5 <SEP> C1 <SEP> C1 <SEP> 1400 <SEP> C/0,001
<tb>  <SEP> 1 <SEP> (Mol.

  <SEP> Dest.)
<tb>  <SEP> Cm <SEP> cm
<tb> 54 <SEP> H5 <SEP> CI <SEP> wCl <SEP> 140  <SEP> C/0,005
<tb>  <SEP>  <  <SEP> (Mol. <SEP> Dest)
<tb>  <SEP> NO2
<tb> sowie <SEP> die <SEP> Verbindungen
<tb> 55 <SEP> 0 <SEP> HC-Br <SEP> Kpo,03 <SEP> 142-1460 <SEP> C
<tb>  <SEP> (CsHsO)2 <SEP> P-O--OCl <SEP> (Mol. <SEP> Dest.)
<tb> 56 <SEP> 0 <SEP> HC-Br <SEP> Ko <SEP> 02 <SEP> 145-1490 <SEP> C
<tb>  <SEP> (C2H50)2P1-0--O2Cl <SEP> (Mol. <SEP> Dest)
<tb>  <SEP> 2P
<tb> 57 <SEP> 0 <SEP> HC-Br <SEP> nicht <SEP> destillierbar
<tb>  <SEP> (C2H50)2P-0--0N02
<tb> 58 <SEP> 0 <SEP> HC-Br <SEP> Kpo2 <SEP> 1380 <SEP> C
<tb>  <SEP> (C2H50)2P-0--0Cl <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> J
<tb> 59 <SEP> 0 <SEP> HC-Br <SEP> Kp0,001 <SEP> 1280 <SEP> C
<tb>  <SEP> (C±Hs0)s <SEP> P-0--0Cl <SEP> (Mol.

  <SEP> Dest.)
<tb>  <SEP> C1
<tb> 60 <SEP> 0 <SEP> HC-Br <SEP> Kr0,02 <SEP> 1401430 <SEP> C
<tb>  <SEP> (C2HsO)2 <SEP> P-0--0 <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> CFs
<tb> 61 <SEP> 0 <SEP> HC-Br <SEP> Kr0,02 <SEP> 107-108  <SEP> C
<tb>  <SEP> (C2H50)2P-o-b-o <SEP> 0( <SEP> Dest)
<tb>  <SEP> C1
<tb>   
EMI8.1     


<tb> 62 <SEP> 0 <SEP> HC-Br <SEP> C <SEP> KPo.02 <SEP> 151  <SEP> C
<tb>  <SEP> (CsHsO)r:8E-oscl <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> Pc:Hs
<tb> 63 <SEP> 0 <SEP> HC-Br <SEP> Kpo,,l <SEP> 1481490 <SEP> C
<tb>  <SEP> C5 <SEP> Ctls <SEP> (Md. <SEP> Dest)
<tb>  <SEP> (C2HsO)2 <SEP> -001 <SEP> Cl
<tb>  <SEP> y
<tb>  <SEP> cí
<tb> 64 <SEP> 0 <SEP> HCCl <SEP> Kp,c, <SEP> 1290 <SEP> C
<tb>  <SEP> iso)CsH7OtOCOt}C1 <SEP> (Mol. <SEP> Dest.)
<tb>  <SEP> 1
<tb> 65 <SEP> O <SEP> HCCl <SEP> Kpo,ol <SEP> 1320 <SEP> C
<tb>  <SEP> (iio) <SEP> C:H7O-0?H > CI <SEP> (Mol. 

  <SEP> Dest)
<tb>  <SEP> c <SEP> r
<tb>  <SEP> Cl
<tb>  



  
 



  Process for the production of new phosphoric acid esters
The present invention relates to a process for the preparation of new phosphoric acid esters of the formula
EMI1.1
 where Hal is chlorine or bromine, Rt and R2 are the same or different and are C-C4-alkyl radicals and R3 is optionally substituted by halogen, C1-C4 alkyl, C-C4 alkoxy, C3-C4 alkylthio, C, -C4 alkylsulfinyl, C1-C4Alkylsullonyl, -NO2, -CF3, -CN, -SCN, -NOs -CFs -CN -SCN
EMI1.2
   -COOAlkyi (C1-C4) or -COOAryl-substituted aryl, in particular phenyl radical, characterized in that

   that a dihaloacetic acid ester of the formula (Hal) 2CH-COOR3 in which Hal is chlorine or bromine and R3 is as defined for formula I, with a trialkyl phosphite of the formula
EMI1.3
 reacted, in which Rt and R2 have the meaning mentioned and R4 is a C-C4-alkyl radical. The reaction can be carried out in a solvent such as toluene, xylene, petroleum ether, dioxane, depending on the speed or sluggishness of the particular reaction.



   This reaction is surprising because in the literature (FW Lichtenthaler, Chem. Rev. 61, 612 [1961]) it is expressly stated to explain the Perkow reaction that the reaction of triethyl phosphite with ethyl dichloroacetate gives only undefined end products in addition to C2HsCl . Dichloroacetic acid esters are said to be unsuitable for the Perkow reaction
Halogen as a substituent of the aryl radical R3 is understood to mean fluorine, chlorine, bromine and iodine.



   Particularly suitable active ingredients are those of the formula I in which Hal is chlorine or bromine, R1 and R2 are methyl or ethyl and R3 is optionally substituted by one or more of the substituents halogen, methyl, methoxy, ethoxy, methylmercapto, methylsulfinyl, methylsulfonyl, -NO2 , -CF3, -CN, -SCN, carbethoxy, carbomethoxy, substituted phenyl group.



   Of these, compounds in which Hal is chlorine and the substituent R3 is a fourth phenyl group substituted by one or more of the substituents chlorine, bromine, iodine, -CN, -NOe or -CF3, which is also methyl or ethyl, have a particularly good effect may contain.



   The new phosphoric acid esters of the formula I act, for example, against insects, nematodes and representatives of the Acarina order, and against phytopathogenic bacteria and fungi. At correspondingly higher application rates, they also show a herbicidal and defoliant effect.



   Its main field of application is the control of all stages of development of sucking and biting insects and acarina, i.e. H. of eggs, larvae, pupae, nymphs and adults or adults.



   Suckling insects include Diptera and Hymenoptera, e.g. B. Aphids (Aphidae) such as Myzus persicae, Doralis fabae, Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solanifolii, Cryptomyzus korschelti, Sappaphis mali, Hyalopterus arundinis, Myzus cerasi, then scale and lice (Coccina), z. B.



  Aspidiotus hederae, Lecanium hesperidum, Pseudococcus maritimus, Thrips species (Thysanoptera) z. B. Hercinothrips femoralis, bed bugs e.g. B. Piesma quadrata, Rhodnius prolixus, Triatoma infestans, cicadas z. B.



  Euscelis bilobatus or Nephotettix bipunctatus.



   Among the biting insects, the Lepidoptera and Coleoptera should be mentioned z. B. Plutella maculipennis, Lymantria dispar, Euproctis chrysorrhoea, Malocosoma neustria, Mamestra brassicae, Agrotis segetum, Pieris brassicae, also Prodenia litura, Ephestia kühniella, Galleria mellonella, then pests of the stockpiling like Dermestolandium castilum and granopharius, Tribusandra castum freshii, Trogoderium castopharius, such as Dermestandra castum zea mais, Stegobium paniceum, Tenebrio molitor, Oryzaephilus surinamensis, Blattela germanica, Periplaneta americana, Blatta orientalis, Blaberus gigantus, Blaberus fuscus, Gryllus domesticus, Sitophilus granarius, Leptinotarsa decemlineata; soil species such as Agriotes sp., Melolontha melolontha; Termites such as Leucotermes reticulitermes sp.



  or Leucotermes flavipes.



   A large number of pests can be found under the order Acarina, e.g. B. mites and especially spider mites (Tetranychidae) such as Tetranychus telarius, T. althaeae, T. urticae, Paratetranychus pilosus, Panonychus ulmi, then gall mites (Eriophyes ribis) and tarsonemids such as Hemitarsonemus latus or Tarsonemus pallidus.



   The order Acarina also includes ticks, i. H. Ectoparasites such as Boophilus microplus Dermanyssus gallinae, Ornithonyssus bacoti, Ornithonyssus sylviarum, Rhipicephalus bursa, Pneumonyssus caninum, Laelaps nutalli, Acarapis woodi, Psorergates ovis.



   This list of pests does not claim to be complete. In principle, the phosphates of the formula I have a strong action against insects and acarina, which are known to be pests in crops of useful plants. For example, the rice stem borer Chilo suppressalis is completely killed off with active ingredient quantities of 0.02 / o.



   In addition to the insecticidal and acaricidal action, the active ingredients of the formula I also have a strong action against phytopathogenic nematodes, of which the following orders should be mentioned:
Aphelenchoides, e.g. B. Aphelenchus ritzemabosi, Aphelenchus fragariae, Aphelenchus oryzae, then Ditylenchoides z. B. Ditylenchus dipsaci, also Meloidogyne, z. B. Meloidogyne arenaria, Meloidogyne incognita, then cyst-forming nematodes (Heterodera), z. B. Heterodera rostochiensis, Heterodera schachtii, then root nematodes such as Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema, Rhadopholus.



   example 1
Production of 0,0-diethyl-1- (4-chlorophenoxy) -2-chloro-vinyl phosphate
EMI2.1

47.6 g of 4-chlorophenyl dichloroacetate were dissolved in 100 ml of toluene. 40 g of triethyl phosphite were added to this solution, whereupon the reaction mixture was heated to 110 ° C. and kept at this temperature for 16 hours.



   The toluene was then drawn off and the crude product was purified using a molecular distillation apparatus.



   Yield 35.3g; Kp: 1000 C / 0.003-0.004 Torr
Analysis for CX2Ht5C1205P calculated: P 9.1 O / o CI 20.8 O / o found: P 8.9 O / o CI 21.3 O / o
The structure of the product was confirmed by means of IR analysis. When SO2Cl2 was added in CH2Cl2, Cl2 was added to the double bond.

  The yellowish trichloroethyl phosphate formed shows the following analytical values for Cl2Ht5a405P: calculated: P 7.52 / o Q 34.42 O / o found: P 7.7 O / o CI 34.9 O / o The following phosphoric acid esters can be obtained in a similar manner :
EMI2.2


<tb> Active ingredient <SEP> Hal <SEP> Rs <SEP> Kp / mmHg
<tb> No. <SEP> R1 = Rn
<tb> 2 <SEP> C2H5 <SEP> CI <SEP> Cl <SEP> 1000 <SEP> C / 0.001
<tb> <SEP> - <SEP> (Md. <SEP> Dest.)
<tb> <SEP> Cl
<tb>
EMI3.1


<tb> Active ingredient <SEP> Hal <SEP> R8 <SEP> Kp / mmHg
<tb> No. <SEP> R1 = R2
<tb> 3 <SEP> CH5 <SEP> C1 <SEP> zuCl <SEP> 1240C / 0.005
<tb> 4 <SEP> CH3 <SEP> CZ <SEP> C1 <SEP> 1300 <SEP> C / 0.001
<tb> <SEP> - <SEP> (Mol.

  <SEP> Dest.)
<tb> <SEP> CF5
<tb> 5 <SEP> CHs <SEP> Cl <SEP> Q¯CFs <SEP> 1300 <SEP> C / 0.001
<tb> <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> C1
<tb> 6 <SEP> CH3 <SEP> CI <SEP> 1¯NOz <SEP> 1350 <SEP> C / 0.001
<tb> <SEP> <<SEP> (Mol. <SEP> Dest.)
<tb> <SEP> CH3
<tb> 7 <SEP> CH3 <SEP> Cl <SEP> / NO2 <SEP> 1350 <SEP> C / 0.001
<tb> <SEP> <<SEP> (Mol. <SEP> Dest.)
<tb> <SEP> C1
<tb> 8 <SEP> C2H5 <SEP> C1 <SEP> - t <SEP> F¯Cl <SEP> 1350 <SEP> C / 0.001
<tb> <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> CFs
<tb> 9 <SEP> C2H5 <SEP> C1 <SEP> ¯ <SEP> / CFa <SEP> 1350 <SEP> C / O, 001
<tb> <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> C1
<tb> 10 <SEP> C2H5 <SEP> Cl <SEP> / N02 <SEP> 1400 <SEP> C / 0.001
<tb> <SEP> - <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> CH3
<tb> 11 <SEP> H5 <SEP> Q <SEP> -4 / <SEP> r <SEP> O2 <SEP> 1300 <SEP> C / 0.001
<tb> <SEP> - <SEP> (Mol.

  <SEP> Dest.)
<tb> <SEP> C1
<tb> 12 <SEP> QH5 <SEP> Cl <SEP> to <SEP> 110 <SEP> C / 0.003
<tb> <SEP> (minor. <SEP> dest.)
<tb> 13 <SEP> C2H5 <SEP> C1 <SEP> to <SEP> 124-1320 <SEP> C / 0.06
<tb> <SEP> Cl
<tb> 14 <SEP> CsH5 <SEP> Cl <SEP> 9 <SEP> 125 <SEP> C / 0.008
<tb> <SEP> Cl
<tb> 15 <SEP> C2H5 <SEP> Cl <SEP> vC1 <SEP> 130 <SEP> C / 0.02
<tb> <SEP> Ci.
<tb>
EMI4.1





  Active ingredient <SEP> Hai <SEP> Ra <SEP> Kp / mmHg
<tb> We} substance <SEP> Hal <SEP> RJ <SEP> Kp / mmHg
<tb> No. <SEP> R = R2
<tb> 16 <SEP> CI <SEP> a <SEP> C1 <SEP> 145 <SEP> C / 0.03
<tb> <SEP> ¸
<tb> 17 <SEP> CsH6 <SEP> Q <SEP>) <SEP> C1 <SEP> 136 "<SEP> C / O, 001
<tb> <SEP> C1 <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> CI
<tb> 18 <SEP> CH1 <SEP> CI <SEP> C1 <SEP> Smp .:

  <SEP> 900 <SEP> C
<tb> <SEP> b
<tb> <SEP> -5Y
<tb> 19 <SEP> c'H1 <SEP> a <SEP> tBr <SEP> 123 <SEP> C / 0.001
<tb> 20 <SEP> ctH5 <SEP> Cl <SEP> 135 "<SEP> C / (>, 003
<tb> <SEP> llr
<tb> 21 <SEP> c'H1 <SEP> Cl <SEP> wO¯CI <SEP> 132137 "<SEP> C / 0.022
<tb> <SEP> C;
<tb> 22 <SEP> H5 <SEP> CI <SEP> CHa <SEP> 115-118 <SEP> C / 0.008
<tb> 23 <SEP> H5 <SEP> CI <SEP> C1 <SEP> not <SEP> desilable
<tb> <SEP> CH,
<tb> 24 <SEP> H5 <SEP> CI <SEP> TABLE <SEP> not <SEP> unlockable
<tb> 25 <SEP> CHi <SEP> a <SEP> tNO2 <SEP> not <SEP> distillable
<tb> 26 <SEP> a <SEP> CI <SEP> CF. <SEP> 130 <SEP> C / 0.002
<tb> <SEP> (Mol. <SEP> Det)
<tb> 27 <SEP> H1 <SEP> CI <SEP> 9 <SEP> 1240 <SEP> C10,015
<tb> <SEP> CHa
<tb> 28 <SEP> C; H5 <SEP> a <SEP> -Ct <SEP> 1300 <SEP> C / 0.02
<tb>
EMI5.1


<tb> Active ingredient <SEP> Hal <SEP> Rs <SEP> Kp / mmHg
<tb> No.

  <SEP> R, = R2
<tb> 29 <SEP> H5 <SEP> Cl <SEP> 9 <SEP> 145-1520 <SEP> C / 0.03
<tb> <SEP> OCH8
<tb> 30 <SEP> C2H5 <SEP> CL <SEP> 9 <SEP> 137-1450 <SEP> C / 0.05
<tb> <SEP> OCHs
<tb> 31 <SEP> H5 <SEP> CI <SEP> OCH3 <SEP> 1650C / o, 02
<tb> 32 <SEP> C2H5 <SEP> CL <SEP> XC1 <SEP> 1420 <SEP> C / 0.015
<tb> <SEP> CH3
<tb> 33 <SEP> H5 <SEP> Cl <SEP> to <SEP> 1400 <SEP> C / 0.001
<tb> <SEP> (Mol. <SEP> (Md. <SEP> Dest.)
<tb> 34 <SEP> H5 <SEP> a <SEP> 9CI <SEP> 1160 <SEP> C / 0.01
<tb> <SEP> C (CHa) 8
<tb> 35 <SEP> C2H5 <SEP> Cl <SEP> COOCH5 <SEP> 1400C / O, 02
<tb> 36 <SEP> C2H5 <SEP> Cl <SEP> 9 <SEP> 13514O0 <SEP> C / O, 02
<tb> <SEP> COOCHs
<tb> 37 <SEP> CH3 <SEP> C1 <SEP> oC1 <SEP> 126 <SEP> C / 0.02
<tb> <SEP> CI
<tb> 38 <SEP> CH3 <SEP> C1 <SEP> C1 <SEP> 1500 <SEP> C / 0.03
<tb> <SEP> ¯C1
<tb> <SEP> C1
<tb> 39 <SEP> CH3 <SEP> Cl <SEP> / Cl <SEP> 1300 <SEP> C / O, 001
<tb> <SEP> - <SEP> (Mol.

  <SEP> Dest.)
<tb> <SEP> Cl
<tb> 40 <SEP> CH3 <SEP> Cl <SEP> yl <SEP> 122 "<SEP> C / 0.02
<tb> <SEP> C1
<tb> 41 <SEP> C2H5 <SEP> Cl <SEP> <2 <SEP> 1300 <SEP> C / O, O2
<tb> <SEP> COOCHs
<tb>
EMI6.1


<tb> Active ingredient <SEP> Hal <SEP> Rs <SEP> Kp / mmHg
<tb> No. <SEP> R1 = R2
<tb> 42 <SEP> H5 <SEP> Cl <SEP> / CN <SEP>, <SEP> 1400 <SEP> C / 0.001
<tb> <SEP> (Md. <SEP> Dest.)
<tb> 43 <SEP> C2Hs <SEP> Cl <SEP> Cl <SEP> 137 <SEP> C / 0.001
<tb> <SEP> (Mol. <SEP> (Mol. <SEP> C1 <SEP> 1370 <SEP> Dest.)
<tb> <SEP> (M. <SEP> Dest.)
<tb> <SEP> Cl
<tb> 44 <SEP> C2H5 <SEP> Cl <SEP> C1 <SEP> Smp .: <SEP> 840 <SEP> C
<tb> <SEP> C1
<tb> 45 <SEP> H5 <SEP> Cl <SEP> CHs <SEP> 1350 <SEP> C / 0.001
<tb> <SEP> cFC <SEP> C1 <SEP> (Ma <SEP> Des.>
<tb> <SEP> C1 <SEP> CHs
<tb> 46 <SEP> H5 <SEP> Cl <SEP> CHs <SEP> 1360 <SEP> C / 0.001
<tb> <SEP> j¸Cl <SEP> (Mol.

  <SEP> Dest.)
<tb> <SEP> C1
<tb> 47 <SEP> C2H <SEP> C1 <SEP> NO2 <SEP> 1300 <SEP> C / 0.001
<tb> <SEP> \ iJ <SEP> (Mon. <SEP> Dest.)
<tb> <SEP> C1
<tb> 48 <SEP> H5 <SEP> C1 <SEP> / Br <SEP> 1350 <SEP> C / 0.005
<tb> <SEP> r <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> OCHs
<tb> 49 <SEP> C2H5 <SEP> Cl <SEP> Cl <SEP> 135 <SEP> C / 0.005
<tb> <SEP> t <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> Br
<tb> 50 <SEP> H5 <SEP> Ci <SEP> -CoCls <SEP> 1800 <SEP> C / 0.08
<tb> 51 <SEP> CH <SEP> Cl <SEP> / CN <SEP> 1250 <SEP> C / O, 001
<tb> <SEP> (Mol. <SEP> Dest.)
<tb> 52 <SEP> H <SEP> Cl <SEP> Br <SEP> 145 <SEP> C / 0.005
<tb> <SEP> ¯Br <SEP> OMoa. <SEP> Dest.)
<tb> <SEP> OCHs
<tb> <SEP> OCHs
<tb>
EMI7.1


<tb> Active ingredient <SEP> Hal <SEP> R3 <SEP> Kp / mmHg
<tb> No. <SEP> R1 = R2
<tb> 53 <SEP> H5 <SEP> C1 <SEP> C1 <SEP> 1400 <SEP> C / 0.001
<tb> <SEP> 1 <SEP> (Mol.

  <SEP> Dest.)
<tb> <SEP> cm <SEP> cm
<tb> 54 <SEP> H5 <SEP> CI <SEP> wCl <SEP> 140 <SEP> C / 0.005
<tb> <SEP> <<SEP> (Mol. <SEP> Dest)
<tb> <SEP> NO2
<tb> and <SEP> the <SEP> connections
<tb> 55 <SEP> 0 <SEP> HC-Br <SEP> Kpo, 03 <SEP> 142-1460 <SEP> C
<tb> <SEP> (CsHsO) 2 <SEP> P-O - OCl <SEP> (Mol. <SEP> dist.)
<tb> 56 <SEP> 0 <SEP> HC-Br <SEP> Ko <SEP> 02 <SEP> 145-1490 <SEP> C
<tb> <SEP> (C2H50) 2P1-0 - O2Cl <SEP> (Mol. <SEP> Dest)
<tb> <SEP> 2P
<tb> 57 <SEP> 0 <SEP> HC-Br <SEP> not <SEP> distillable
<tb> <SEP> (C2H50) 2P-0-0N02
<tb> 58 <SEP> 0 <SEP> HC-Br <SEP> Kpo2 <SEP> 1380 <SEP> C
<tb> <SEP> (C2H50) 2P-0--0Cl <SEP> (Mol. <SEP> dist.)
<tb> <SEP> J
<tb> 59 <SEP> 0 <SEP> HC-Br <SEP> Kp0.001 <SEP> 1280 <SEP> C
<tb> <SEP> (C ± Hs0) s <SEP> P-0--0Cl <SEP> (Mol.

  <SEP> Dest.)
<tb> <SEP> C1
<tb> 60 <SEP> 0 <SEP> HC-Br <SEP> Kr0.02 <SEP> 1401430 <SEP> C
<tb> <SEP> (C2HsO) 2 <SEP> P-0--0 <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> CFs
<tb> 61 <SEP> 0 <SEP> HC-Br <SEP> Kr0.02 <SEP> 107-108 <SEP> C
<tb> <SEP> (C2H50) 2P-o-b-o <SEP> 0 (<SEP> Dest)
<tb> <SEP> C1
<tb>
EMI8.1


<tb> 62 <SEP> 0 <SEP> HC-Br <SEP> C <SEP> KPo.02 <SEP> 151 <SEP> C
<tb> <SEP> (CsHsO) r: 8E-oscl <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> Pc: Hs
<tb> 63 <SEP> 0 <SEP> HC-Br <SEP> Kpo ,, l <SEP> 1481490 <SEP> C
<tb> <SEP> C5 <SEP> Ctls <SEP> (Md. <SEP> Dest)
<tb> <SEP> (C2HsO) 2 <SEP> -001 <SEP> Cl
<tb> <SEP> y
<tb> <SEP> cí
<tb> 64 <SEP> 0 <SEP> HCCl <SEP> Kp, c, <SEP> 1290 <SEP> C
<tb> <SEP> iso) CsH7OtOCOt} C1 <SEP> (Mol. <SEP> Dest.)
<tb> <SEP> 1
<tb> 65 <SEP> O <SEP> HCCl <SEP> Kpo, ol <SEP> 1320 <SEP> C
<tb> <SEP> (iio) <SEP> C: H7O-0? H> CI <SEP> (Mol.

  <SEP> Dest)
<tb> <SEP> c <SEP> r
<tb> <SEP> Cl
<tb>

Claims (1)

PATENTANSPRUCH Verfahren zur Herstellung von Verbindungen der Formel EMI8.2 worin Hal Chlor oder Brom bedeutet, R1 und R2 gleich oder verschieden sind und C1-C4-Alkylreste bedeuten und R5 ein gegebenenfalls durch Halogen, C1-C4 Alkyl, C1C4 Alkoxy, Cl-C4 Alkylthio, C1C4 Alkyl sulfinyl-, C-C4-Alkylsulfonyl, -NO2, -CF,, CN, -SCN, -NO1 -CF2 -CN -SCN EMI8.3 COOAlkyl(C,-C4) oder -COOAryl substituiertes Aryladikal darstellt, dadurch gekennzeichnet, dass man innen Dihalogenessigsäureester der Formel (Hal)sCH-COO Rs worin Hal Chlor oder Brom bedeutet und R" die oben erwähnte Bedeutung zukommt, PATENT CLAIM Process for the preparation of compounds of the formula EMI8.2 where Hal is chlorine or bromine, R1 and R2 are identical or different and are C1-C4-alkyl radicals and R5 is optionally substituted by halogen, C1-C4 alkyl, C1C4 alkoxy, Cl-C4 alkylthio, C1C4 alkyl sulfinyl, C-C4- Alkylsulfonyl, -NO2, -CF ,, CN, -SCN, -NO1 -CF2 -CN -SCN EMI8.3 COOAlkyl (C, -C4) or -COOAryl-substituted aryl radical, characterized in that inside dihaloacetic acid ester of the formula (Hal) sCH-COO Rs where Hal is chlorine or bromine and R "has the meaning mentioned above, mit einem Trialkylphosphit der Formel EMI8.4 umsetzt, worin R1 und R2 die erwähnte Bedeutung haben und R4 eilen C1-4 Alkylrest darstellt. with a trialkyl phosphite of the formula EMI8.4 converts, in which R1 and R2 have the meaning mentioned and R4 is a C1-4 alkyl radical. UNTERANSPRÜCHE 1. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI8.5 2. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI8.6 3. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI9.1 4. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI9.2 5. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI9.3 6. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI9.4 7. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI9.5 8. Verfahren gemäss Patentanspruch zur Herstellung der Verbindung der Formel EMI9.6 SUBCLAIMS 1. Process according to claim for the preparation of the compound of the formula EMI8.5 2. Process according to claim for the preparation of the compound of the formula EMI8.6 3. Process according to claim for the preparation of the compound of the formula EMI9.1 4. Process according to claim for the preparation of the compound of the formula EMI9.2 5. Process according to claim for the preparation of the compound of the formula EMI9.3 6. Process according to claim for the preparation of the compound of the formula EMI9.4 7. Process according to claim for the preparation of the compound of the formula EMI9.5 8. Process according to claim for the preparation of the compound of the formula EMI9.6
CH1255369A 1969-08-18 1969-08-18 New insecticidal phosphoric esters CH516595A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
BE754922D BE754922A (en) 1969-08-18 NEW PHOSPHORIC ESTERS, THEIR PREPARATION PROCESS AND THEIR USE AS PESTICIDAL AGENTS
CH1255369A CH516595A (en) 1969-08-18 1969-08-18 New insecticidal phosphoric esters
CH1490871A CH528865A (en) 1969-08-18 1969-08-18 New insecticidal phosphoric esters
DE19702039529 DE2039529A1 (en) 1969-08-18 1970-08-08 New phosphoric acid esters, their production and use
FR7029560A FR2056852A5 (en) 1969-08-18 1970-08-11
IL35116A IL35116A0 (en) 1969-08-18 1970-08-14 Phosphoric acid esters,their preparation and use as pesticides
US00064648A US3732343A (en) 1969-08-18 1970-08-17 1-halo-2-aryloxy-vinyl (2)-phosphates
NL7012129A NL7012129A (en) 1969-08-18 1970-08-17
ZA705638A ZA705638B (en) 1969-08-18 1970-08-17 Phosphoric acid esters,their preparation and use as pesticides
ES382810A ES382810A1 (en) 1969-08-18 1970-08-17 1-halo-2-aryloxy-vinyl (2)-phosphates
GB3975370A GB1321087A (en) 1969-08-18 1970-08-18 Phosphoric acid esters their preparation and use as pesticides
US00332470A US3852438A (en) 1969-08-18 1973-02-14 Pesticidal compositions containing 1-halo-2-aryloxy-vinyl-(2)-phosphates
US00332469A US3840660A (en) 1969-08-18 1973-02-14 Control of plant pathogenic fungi with 1-halo-2-aryloxy-vinyl-(2)phosphates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1255369A CH516595A (en) 1969-08-18 1969-08-18 New insecticidal phosphoric esters

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CH516595A true CH516595A (en) 1971-12-15

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CH1490871A CH528865A (en) 1969-08-18 1969-08-18 New insecticidal phosphoric esters
CH1255369A CH516595A (en) 1969-08-18 1969-08-18 New insecticidal phosphoric esters

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CH1490871A CH528865A (en) 1969-08-18 1969-08-18 New insecticidal phosphoric esters

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CH (2) CH528865A (en)
ZA (1) ZA705638B (en)

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CH528865A (en) 1972-10-15
ZA705638B (en) 1971-06-30

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