DE2003561A1 - New phosphoric acid esters, their production and the compositions containing them - Google Patents
New phosphoric acid esters, their production and the compositions containing themInfo
- Publication number
- DE2003561A1 DE2003561A1 DE19702003561 DE2003561A DE2003561A1 DE 2003561 A1 DE2003561 A1 DE 2003561A1 DE 19702003561 DE19702003561 DE 19702003561 DE 2003561 A DE2003561 A DE 2003561A DE 2003561 A1 DE2003561 A1 DE 2003561A1
- Authority
- DE
- Germany
- Prior art keywords
- general formula
- phosphoric acid
- atom
- acid esters
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 16
- 150000003014 phosphoric acid esters Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 3
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 230000000895 acaricidal effect Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical compound N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- BLNWTAHYTCHDJH-UHFFFAOYSA-O hydroxy(oxo)azanium Chemical compound O[NH+]=O BLNWTAHYTCHDJH-UHFFFAOYSA-O 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000003453 indazolyl group Chemical class N1N=C(C2=C1C=CC=C2)* 0.000 claims 1
- 239000002917 insecticide Substances 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 amine salt Chemical class 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000002473 indoazoles Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- REHRQXVEAXFIML-UHFFFAOYSA-N 1h-indazole-3-carbonitrile Chemical compound C1=CC=C2C(C#N)=NNC2=C1 REHRQXVEAXFIML-UHFFFAOYSA-N 0.000 description 2
- QPHAGNNWDZSKJH-UHFFFAOYSA-N 3-chloro-2h-indazole Chemical compound C1=CC=CC2=C(Cl)NN=C21 QPHAGNNWDZSKJH-UHFFFAOYSA-N 0.000 description 2
- UOWPRWCAMGTPHI-UHFFFAOYSA-N 3-chloro-5-nitro-2h-indazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNC(Cl)=C21 UOWPRWCAMGTPHI-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- MTQKMPGBALVEDL-ZPCKWCKBSA-N (z,12r)-12-hydroxy-2-sulfooctadec-9-enoic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCC(C(O)=O)S(O)(=O)=O MTQKMPGBALVEDL-ZPCKWCKBSA-N 0.000 description 1
- UQDREBLIFYDUTG-UHFFFAOYSA-N 1-(hydroxymethyl)indazole-3-carbonitrile Chemical compound OCN1N=C(C2=CC=CC=C12)C#N UQDREBLIFYDUTG-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- XODZPAYJXYWLJC-UHFFFAOYSA-N 5-chloro-1-(chloromethyl)indazole-3-carbonitrile Chemical compound ClCN1N=C(C2=CC(=CC=C12)Cl)C#N XODZPAYJXYWLJC-UHFFFAOYSA-N 0.000 description 1
- FVNCILPDWNBPLK-UHFFFAOYSA-N 5-chloro-1h-indazole Chemical compound ClC1=CC=C2NN=CC2=C1 FVNCILPDWNBPLK-UHFFFAOYSA-N 0.000 description 1
- QMIBICADHKQAJK-UHFFFAOYSA-N 5-chloro-1h-indazole-3-carbonitrile Chemical compound ClC1=CC=C2NN=C(C#N)C2=C1 QMIBICADHKQAJK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- HYTRYEXINDDXJK-UHFFFAOYSA-N Ethyl isopropyl ketone Chemical compound CCC(=O)C(C)C HYTRYEXINDDXJK-UHFFFAOYSA-N 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 101000713575 Homo sapiens Tubulin beta-3 chain Proteins 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000006725 Meisenheimer rearrangement reaction Methods 0.000 description 1
- 241000238814 Orthoptera Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 102100036790 Tubulin beta-3 chain Human genes 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003218 pyrazolidines Chemical class 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- 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
- C07F9/645—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
- C07F9/65038—Five-membered rings having the nitrogen atoms in the positions 1 and 2 condensed with carbocyclic rings or carbocyclic ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Dr. F. Zumstein jun.Dr. F. Zumstein jun.
PatentanwältePatent attorneys
SQ 3495SQ 3495
RHGNE-POULENG S.A,, Paris/PrankreichRHGNE-POULENG S.A ,, Paris / France
ϊ^ΐ ΪΪ5 iSv Sv* «Sm SS> SkB SvV «vw ΐη* <■■■! ΐϊΐ ISi ΐΐν avB SS 4ϊ ^ ΐ ΪΪ5 iSv Sv * «Sm SS> SkB SvV «vw ΐη * <■■■! ΐϊΐ ISi ΐΐν avB SS 4
ϊΐ ΪΪΕ ΐνΐ ΐ^ΐ «MV S^» ΐ!ΐ SSl^dS ^SSi HH ■£■* SS hbS Sa? SaU «feS SSrϊΐ ΪΪΕ ΐνΐ ΐ ^ ΐ «MV S ^» ΐ! ΐ SSl ^ dS ^ SSi HH ■ £ ■ * SS hbS Sa? SaU «feS SSr
Neue Phosphorsäureester, ihre HerstellungNew phosphoric acid esters, their production
und die sie enthaltenden Mitteland the agents containing them
Die vorliegende Erfindung betrifft neue Phosphorsäureester der allgemeinen FormelThe present invention relates to new phosphoric acid esters the general formula
-S-P-S-P
C2%" C 2% "
deren Herstellung sowie die Zusammensetzungen, die diese enthalten.their manufacture as well as the compositions that make them contain.
In der obigen allgemeinen Formel I bedeutet R.. ein Halogen· atom., vorzugsweise ein Chloratom, oder einen Cyanorest, Rp stellt ein Wasserstoffätom oder ein Halogenatom, vorzugsweise ein Chloratom, oder einen Nitrorest dar, und R, und Rj,, die gleich oder voneinander verschieden sein können, bedeuten jeweils ein Wasserstoffatom oder ein Halogenatom, vorzugsweise ein Chloratom.In the above general formula I, R .. denotes a halogen · atom., preferably a chlorine atom, or a cyano radical, Rp represents a hydrogen atom or a halogen atom, preferably represents a chlorine atom, or a nitro radical, and R, and Rj ,, which can be the same or different from each other, each represent a hydrogen atom or a halogen atom, preferably a chlorine atom.
009831/1937009831/1937
Erfindungsgem'äss können diese neuen Phosphorsäureester durch Umsetzung eines Phosphorderivats der allgemeinen Formel According to the invention, these new phosphoric esters can by reacting a phosphorus derivative of the general formula
MS-PMS-P
O C2H5 OC 2 H 5
O C2H5 OC 2 H 5
(II)(II)
in der M ein Alkalimetallatom oder ein Aimnoniumion bedeutet, mit einem Indazolderivat der allgemeinen Formelin which M is an alkali metal atom or an ammonium ion, with an indazole derivative of the general formula
(III)(III)
in der R1 i Rp, R, und R1, die oben angegebenen Bedeutungen besitzen und Y einen reaktionsfähigen Esterrest, wie beispielsweise ein Halogenatom oaer einen Schwefelsäure- oder SuIfonsäureesterrest, darstellt, hergestellt werden.in which R 1 , Rp, R, and R 1 have the meanings given above and Y is a reactive ester radical, such as, for example, a halogen atom or a sulfuric acid or sulfonic acid ester radical.
Das Derivat der allgemeinen Formel II wird in Form eines Alkalisalzes, das gegebenenfalls in situ hergestellt wird, oder eines Ammonium- oder Aminsalzes verwendet.The derivative of the general formula II is in the form of an alkali salt, which is optionally prepared in situ, or an ammonium or amine salt is used.
Die Reaktion wird vorzugsweise in einem organischen Lösungsmittel, insbesondere in einem Alkohol, wie beispielsweiseThe reaction is preferably carried out in an organic solvent, especially in an alcohol such as
009831/1937009831/1937
Äthanol, einem Keton, wie beispielsweise Aceton oder Methyl· äthylketon, einem Ester, wie beispielsweise Kthylacetat, einem Nitril, wie beispielsweise Acetonitril, oder einem aromatischen Kohlenwasserstoff> wie beispielsweise Benzol, bei einer Temperatur zwischen gewöhnlicher.Temperatur und 1000C durchgeführt.Ethanol, a ketone such as acetone or methyl ethyl ethyl ketone, an ester, such as Kthylacetat, a nitrile such as acetonitrile or an aromatic hydrocarbon> such as benzene, carried out at a temperature between gewöhnlicher.Temperatur and 100 0 C.
Die.Produkte der allgemeinen Formel III können aus Indazolr derivaten der allgemeinen FormelDie.Produkte of the general formula III can be made from Indazolr derivatives of the general formula
(IV)(IV)
in der R-,in the R-,
Rp, R, undRp, R, and
die oben angegebenen Bedeutungen
besitzen, durch Hydroxymethylierung mit Formaldehyd und anschliessende Umwandlung des Hydroxyrests in einen reaktiven
Esterrest hergestellt werden. 'the meanings given above
have, by hydroxymethylation with formaldehyde and subsequent conversion of the hydroxy group into a reactive ester group. '
Die Indazolderivate der allgemeinen Formel IV^ können nach
einer der in "The Chemistry of Heterocyclic. Compounds
(Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and
Condensed Rings), A. Weissberger, Edit.. Interscience Publishers, Part 5ϊ 289-382 (1967)" beschriebenen Methoden erhalten werden
.The indazole derivatives of the general formula IV ^ can according to one of the in "The Chemistry of Heterocyclic. Compounds
(Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and
Condensed Rings), A. Weissberger, Edit. Interscience Publishers, Part 5ϊ 289-382 (1967) "methods described.
Die neuen Phosphorsäureester der allgemeinen Formel I weisen
bemerkenswerte insektlcide und acaricide Eigenschaften
auf. Sie sind durch Kontakt oder direkte Aufnahme wirksam.The new phosphoric acid esters of the general formula I have remarkable insecticidal and acaricidal properties
on. They are effective through contact or direct intake.
009831/1937009831/1937
,·: υ ■ 3 5 6 1, ·: Υ ■ 3 5 6 1
Sie haben sich als besonders wirksam bei den Dipteren, Coleopteren, Hemipteren, Lepidopteren, Orthopteren und Acarinen erwiesen.They have proven to be particularly effective in the dipteras, Coleoptera, Hemiptera, Lepidoptera, Orthoptera and Acarines have been shown.
Unter den Produkten der allgemeinen Formel I sind diejenigen besonders interessant, für welche R. ein Halogenatom oder einen Cyanorest bedeutet, PU ein Halogenatom darstellt und R, und R1, Wasserstoff atome bedeuten. Ganz besonders seien noch die folgenden Produkte genannt:Among the products of the general formula I, those are of particular interest for which R. is a halogen atom or a cyano radical, PU is a halogen atom and R and R 1 are hydrogen atoms. The following products should be mentioned in particular:
1-(0,0-Diäthyldithiophosphorylmethyl)-;5,5-dichlorindazol i-COjO-DiäthyldithiophosphorylmethylJ-^-cyano-S-chlorindazol1- (0,0-diethyldithiophosphorylmethyl) -; 5,5-dichloroindazole i-COjO-diethyldithiophosphorylmethylJ - ^ - cyano-S-chlorindazole
Die vorliegende Erfindung betrifft auch die in der Landwirtschaft verwendbaren insekticiden und acariciden Zusammensetzungen, die als wirksames Produkt zumindest einen Phosphorsäureester der allgemeinen Formel I zusammen mit einem oder mehreren Verdünnungsmitteln oder Adjuvantien, die mit dem oder den wirksamen Produkten -verträglich und für die Verwendung in der Landwirtschaft geeignet sind, enthalten. In diesen Zusammensetzungen kann der Gehalt an wirksamem Produkt zwischen 0,005 und 80 Gew.-# betragen.The present invention also relates to the insecticidal and acaricidal compositions which can be used in agriculture, which as an effective product at least one phosphoric acid ester of the general formula I together with one or more diluents or adjuvants compatible with the active product or products and suitable for use are suitable in agriculture. In these compositions, the content of the active product between 0.005 and 80 wt .- #.
Die Zusammensetzungen können in fester Form vorliegen, wenn man ein festes pulverförmiges verträgliches Verdünnungsmittel, wie beispielsweise Talcum, calcinierte Magnesia, Kieselgur ,Tricalciurnphosphat, Korkpulver, Adsorptionskohle oder auch einen Ton, wie beispielsweise Kaolin oder Bentonit, verwendet. Die festen Zusammensetzungen werden vorteilhafterweise durch Zerkleinern der wirksamen Verbindung mit dem festen Verdünnungsmittel oder durch Imprägnieren des festen Verdünnungsmittels mit einer Lösung der wirksamen Verbindung in einem flüchtigen Lösungsmittel, Verdampfen des Lösungsmittels und erforderlichenfalls Zerkleinern des Produkts zur Erzielung eines Pulvers hergestellt.The compositions can be in solid form if a solid powdery compatible diluent, such as talc, calcined magnesia, kieselguhr, tricalcium phosphate, cork powder, adsorption carbon or a clay, such as kaolin or bentonite, is used. The solid compositions are advantageous by crushing the active compound with the solid diluent or by impregnating the solid Diluent with a solution of the active compound in a volatile solvent, evaporation of the solvent and, if necessary, crushing the product to obtain a powder.
009831/1937009831/1937
ORIGINAL INSPECTEDORIGINAL INSPECTED
Man kann auch flüssige Zusammensetzungen unter Verwendung eines flüssigen Verdünnungsmittels erhalten, in welchem das erfindungsgemässe Produkt oder die erfindungsgemässen Produkte gelöst oder dispergiert ist oder sind. Die Zusammensetzungen können in Form einer Suspension", einer Emulsion oder einer Lösung in einem organischen oder wässrigorganischen Medium vorliegen. Die Zusammensetzungen in Form von Dispersionen,'Lösungen oder Emulsionen können Netzmittel, Dispergiermittel oder Emulgiermittel des ionischen oder nichtionischen Typs, wie beispielsweise Sulforicinoleate,-quaternäre Ammoniumsalze oder Produkte auf der Basis von Äthy- λ lenoxydkondensaten, wie beispielsweise die Kondensate von ™ Äthylenoxyd mit Octylphenol, oder Fettsäureester von Anhydrosorbiten, die durch Verätherung der freien Hydroxylgruppen durch Kondensation mitKthylenoxyd löslieh gemacht sind, enthalten. Es ist bevorzugt, Mittel vom nicht-ionischen Typ zu verwenden, da diese gegenüber Elektrolyten nicht empfindlich sind. Wenn man Emulsionen wünscht, können die erfindungsgemässen Phosphorsäureester in Form von selbstemulgierbaren Konzentraten verwendet werden, die die Wirksubstanz, gelöst in einem Dispergiermittel oder in einem mit diesem Mittel verträglichen Lösungsmittel enthalten, wobei eine einfache Zugabe von Wasser ermöglicht,gebrauchsfertige Zusammensetzungen zu erhalten. - '.""'■ iLiquid compositions can also be obtained using a liquid diluent in which the product or products according to the invention is or are dissolved or dispersed. The compositions can be in the form of a suspension, an emulsion or a solution in an organic or aqueous-organic medium. The compositions in the form of dispersions, solutions or emulsions can be wetting agents, dispersants or emulsifiers of the ionic or nonionic type, such as, for example, sulforicinoleate, - Quaternary ammonium salts or products based on Äthy- λ lenoxydkondensaten, such as the condensates of ™ Äthylenoxyd with octylphenol, or fatty acid esters of anhydrosorbites, which are made soluble by etherification of the free hydroxyl groups by condensation withKthylenoxid. It is preferred to not contain agents -ionic type, since they are not sensitive to electrolytes.If you want emulsions, the phosphoric acid esters according to the invention can be used in the form of self-emulsifiable concentrates, the active substance, dissolved in a dispersant or in a mi t contain solvent compatible with this agent, and a simple addition of water enables ready-to-use compositions to be obtained. - '. ""' ■ i
Die neuen Phosphorsäureester der allgemeinen Formel I werden vorzugsweise in einer Menge von 5 bis 200 g Wirksubstanz je Hektoliter Wasser verwendet.The new phosphoric acid esters of the general formula I are preferably used in an amount of 5 to 200 g of active ingredient per hectolitre of water.
Die folgenden Beispiele erläutern die Erfindung, ohne sie zu beschränken* 'The following examples illustrate the invention without it to restrict * '
00 9 831/193700 9 831/1937
. 6 - :: u ü 3 S 61. 6 - :: u ü 3 S 61
Zu einer Lösung von 14 g 1-Chlorinethyl-3-chlor-5-nitroindazol in 100 cnr Aceton setzt man 12,8 g Ammonium-OiO-diäthyldithiophosphat zu. Man rührt 8 Stunden bei etwa 25°C. Der gebildete Niederschlag wird abfiltriert und das Aceton unter vermindertem Druck verdampft. Das zurückbleibende öl wird in 150 cnr Methylenchlorid aufgenommen und die erhaltene Lösung wird nacheinander mit 150 cnr destilliertem Wasser, 150 cnr einer wässrigen 10 $igen (Gewicht je Volumen) Kaliumbicarbonatlösung und I50 cnr destilliertem Wasser gewaschen. Nach Trocknen über wasserfreiem Natriumsulfat, Behandlung mit Entfärbungskohle und Einengen unter vermindertem Druck erhält man 19g 1-(0,0-Diäthyldithiophosphorylmethyl)-5-chlor-5-nitroindazol vom F = 50°C.To a solution of 14 g of 1-chloroethyl-3-chloro-5-nitroindazole 12.8 g of ammonium-OiO-diethyldithiophosphate are placed in 100 cnr of acetone to. The mixture is stirred at about 25 ° C. for 8 hours. The precipitate formed is filtered off and the acetone under evaporated under reduced pressure. The remaining oil is taken up in 150 cnr methylene chloride and the resulting solution is successively mixed with 150 cnr of distilled water, 150 cnr of an aqueous 10 $ (weight per volume) potassium bicarbonate solution and 150 cnr distilled water. After drying over anhydrous sodium sulfate, treatment with Decolorizing charcoal and concentration under reduced pressure gives 19 g of 1- (0,0-diethyldithiophosphorylmethyl) -5-chloro-5-nitroindazole from F = 50 ° C.
Das als Ausgangsprodukt verwendete 1-Chlorine thyl-3-chlor-5-nitroindazol vom F = 1100C wird durch Umsetzung von Thionylchlorid mit 1-Hydroxymethyl-5-chlor-5-nitroindäzol vom F = 18O°C erhalten, welch letzteres durch Einwirkung von Formaldehyd auf 3-Chlor-5-nitroindazol vom F = 122°C hergestellt wird. Das 3-Chlor-5-nitroindazol wird durch Nitrierung von 3-Chlorindazol erhalten., Das 3-Chlorindazol vom F = 149°C wird nach dem von E. STEPHENSON, Org. Synth., 2£, 55 (19^9) beschriebenen Verfahren hergestellt.The 1-chlorinethyl-3-chloro-5-nitroindazole used as the starting product from F = 110 0 C is obtained by reacting thionyl chloride with 1-hydroxymethyl-5-chloro-5-nitroindazole from F = 180 ° C, the latter by Action of formaldehyde on 3-chloro-5-nitroindazole from the temperature = 122 ° C is produced. The 3-chloro-5-nitroindazole is obtained by nitration of 3-chloroindazole., The 3-chloroindazole with a melting point of 149 ° C is obtained according to the method described by E. STEPHENSON, Org. Synth., 2 £, 55 (19 ^ 9) described method produced.
Zu einer Lösung von 15*3 S 1-Chlormethyl-J-cyanoindazol in 200 cnr Aceton setzt man 16,5 g Ammonium-OjO-diäthyldithiophosphat zu. Man rührt 8 Stunden bei etwa 25°C. Der gebildete Niederschlag wird abfiltriert und das Aceton unter ver- 16.5 g of ammonium OjO-diethyldithiophosphate are added to a solution of 15 * 3 S 1-chloromethyl-I-cyanoindazole in 200 cnr acetone. The mixture is stirred at about 25 ° C. for 8 hours. The precipitate formed is filtered off and the acetone under
- 009831/1937 iAI - 009831/1937 iAI
ORIGINALORIGINAL
mindertem Druck verdampft. Die zurückgebliebene Festsubstanz liefert nach Umkristallisieren aus Äthanol 22 g 1-(0,0-Diäthyldithiophosphorylmethyl)-3-cyanoindazol vom F = 660C.evaporated under reduced pressure. The remaining solid after recrystallization from ethanol gives 22 g of 1- (0,0-Diäthyldithiophosphorylmethyl) -3-cyanoindazol from F = 66 0 C.
Das als Ausgangsprodukt verwendete 1-Chlorinethy 1-3-cyanoindazol wird durch Umsetzung von Thionylchlorid mit 1-Hydroxymethyl-3-cyanoindazol vom F=16O°C erhalten, welch letzteres durch Einwirkung von Formaldehyd auf 3-Cyanoindazol hergestellt wird.The 1-Chlorinethy 1-3-cyanoindazole used as the starting product is made by reacting thionyl chloride with 1-hydroxymethyl-3-cyanoindazole obtained from F = 160 ° C, the latter produced by the action of formaldehyde on 3-cyanoindazole will.
Das 3-Cyanoindazol vom F = 14O°C wird nach dem von J. MEISEN-HEIMER u. Mitarb., Ber. 57B, 1715 (1924) beschriebenen Verfahren hergestellt.The 3-cyanoindazole with an temperature of 140 ° C is made according to the method described by J. MEISEN-HEIMER and colleagues, Ber. 57B, 1715 (1924) manufactured.
Nach der in Beispiel 1 beschriebenen Arbeitsweise stellt man aus den geeigneten Ausgangsmaterialien die Produkte der Formel I, für welche die Symbole die in der nachfolgenden Tabelle angegebenen Bedeutungen besitzen, her:According to the procedure described in Example 1, one sets from the suitable starting materials, the products of the formula I for which the symbols are those in the table below have given meanings, from:
009831/1937009831/1937
1U υ 3 5 6 1 1 U υ 3 5 6 1
3eispiel 3example 33
Zu einer Lösung von 8 g i-Chlormethyl-^-cyano^-chlorindazol in 150 cnr Aceton setzt man 7*1 g Ammonium-0,0-diäthyldithiophosphat zu. Man rührt 6 Stunden bei etwa 25°C. Der gebildete Niederschlag wird abfiltriert und das Aceton unter vermindertem Druck verdampft. Das zurückbleibende öl wird in 200 cnr Methylenchlorid aufgenommen und die erhaltene Lösung wird nacheinander mit 100 cnr destilliertem Wasser, 100 cnr einer wässrigen 0,4 #igen (Gewicht je Volumen) Natriumhydroxydlösung und 100 cnr destilliertem Wasser gewaschen. Nach Trocknen über wasserfreiem Natriumsulfat, Behandlung mit Entfärbungskohle und Einengen unter vermindertem Druck erhält man nach Umkristallisation aus Äthanol 7 g 1-(0,0-Diäthyldithiophosphorylmethyl)-3-cyano-5-chlorindazol vom P « 700C.7 * 1 g of ammonium 0,0-diethyldithiophosphate are added to a solution of 8 g of i-chloromethyl- ^ - cyano ^ -chlorindazole in 150 cnr acetone. The mixture is stirred at about 25 ° C. for 6 hours. The precipitate formed is filtered off and the acetone is evaporated off under reduced pressure. The remaining oil is taken up in 200 cnr methylene chloride and the resulting solution is washed successively with 100 cnr distilled water, 100 cnr an aqueous 0.4 # (weight per volume) sodium hydroxide solution and 100 cnr distilled water. After drying over anhydrous sodium sulfate, treatment with decolorizing and concentration under reduced pressure gives after recrystallization from ethanol, 7 g of 1- (0,0-Diäthyldithiophosphorylmethyl) -3-cyano-5-chlorindazol P "70 0 C.
Das als Ausgangssubstanz verwendete 1-Chlormethyl-3-cyano-5-chlorindazol vom F = 1500C wird durch Umsetzung von Thionylchlorid mit i-Hydroxymethyl-J-cyano-S-ohlorlndazol vom F - 18O°C erhalten, welch letzteres durch Einwirkung von Formaldehyd auf 3-Cyano~5-chlorindazol vom F = 4o°C hergestellt wird. Das 3-Cyano-5-chlorindazol wird durch Umsetzung von Natriumchlorat mit J-Cyanoindazol hergestellt.Used as a starting material 1-chloromethyl-3-cyano-5-chlorindazol from F = 150 0 C is prepared by reacting thionyl chloride with i-hydroxymethyl-J-cyano-S-ohlorlndazol from F - obtained 18O ° C, the latter what by action from formaldehyde to 3-cyano ~ 5-chloroindazole with a temperature of 40 ° C. 3-Cyano-5-chloroindazole is produced by reacting sodium chlorate with J-cyanoindazole.
Zu einer Lösung von 25 Teilen 1-(0,0-Diäthyldithiophosphoryl· methyl)-^-chlor-S-nitroindazol in 65 Teilen eines Gemische gleicher Teile Toluol und Acetophenon setzt man 10 Teile eines Kondensationsprodukts von Octylphenol und Äthylenoxyd in einem Verhältnis von 10 Molekülen Äthylenoxyd je Molekül Octylphenol zu. Die erhaltene Lösung wird nach Verdünnen mit Wasser in einer Menge von 200 cnr dieser Lösung je 100 1 Wasser verwendet. 009831/1937To a solution of 25 parts of 1- (0,0-diethyldithiophosphoryl methyl) - ^ - chloro-S-nitroindazole in 65 parts of a mixture 10 parts are used in equal parts of toluene and acetophenone a condensation product of octylphenol and ethylene oxide in a ratio of 10 ethylene oxide molecules per molecule Octylphenol too. The solution obtained is diluted with water in an amount of 200 cnr of this solution per 100 liters of water used. 009831/1937
Original inspectedOriginal inspected
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR6901551A FR2033176A1 (en) | 1969-01-27 | 1969-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2003561A1 true DE2003561A1 (en) | 1970-07-30 |
Family
ID=9028232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19702003561 Pending DE2003561A1 (en) | 1969-01-27 | 1970-01-27 | New phosphoric acid esters, their production and the compositions containing them |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5030700B1 (en) |
| AT (1) | AT298154B (en) |
| BE (1) | BE744962A (en) |
| CH (1) | CH507657A (en) |
| DE (1) | DE2003561A1 (en) |
| EG (1) | EG11116A (en) |
| ES (1) | ES375924A1 (en) |
| FR (1) | FR2033176A1 (en) |
| GB (1) | GB1237664A (en) |
| IL (1) | IL33781A (en) |
| LU (1) | LU60228A1 (en) |
| NL (1) | NL7000717A (en) |
| OA (1) | OA03407A (en) |
-
1969
- 1969-01-27 FR FR6901551A patent/FR2033176A1/fr not_active Withdrawn
-
1970
- 1970-01-19 NL NL7000717A patent/NL7000717A/xx unknown
- 1970-01-20 OA OA53839A patent/OA03407A/en unknown
- 1970-01-23 GB GB3490/70A patent/GB1237664A/en not_active Expired
- 1970-01-23 JP JP45005766A patent/JPS5030700B1/ja active Pending
- 1970-01-26 CH CH104570A patent/CH507657A/en not_active IP Right Cessation
- 1970-01-26 BE BE744962D patent/BE744962A/en unknown
- 1970-01-26 LU LU60228D patent/LU60228A1/xx unknown
- 1970-01-26 IL IL33781A patent/IL33781A/en unknown
- 1970-01-27 ES ES375924A patent/ES375924A1/en not_active Expired
- 1970-01-27 AT AT72970A patent/AT298154B/en not_active IP Right Cessation
- 1970-01-27 DE DE19702003561 patent/DE2003561A1/en active Pending
-
1974
- 1974-09-15 EG EG395/74A patent/EG11116A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| OA03407A (en) | 1970-12-15 |
| ES375924A1 (en) | 1972-04-16 |
| NL7000717A (en) | 1970-07-29 |
| JPS5030700B1 (en) | 1975-10-03 |
| GB1237664A (en) | 1971-06-30 |
| BE744962A (en) | 1970-07-27 |
| CH507657A (en) | 1971-05-31 |
| IL33781A0 (en) | 1970-03-22 |
| AT298154B (en) | 1972-04-25 |
| FR2033176A1 (en) | 1970-12-04 |
| LU60228A1 (en) | 1970-07-29 |
| EG11116A (en) | 1977-04-30 |
| IL33781A (en) | 1972-09-28 |
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