CA1115275A - N-iso-propyl-s-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl- methyl)- thiolphosphoric acid ester-amides, a process for their preparation and their use as agents for combating pests - Google Patents
N-iso-propyl-s-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl- methyl)- thiolphosphoric acid ester-amides, a process for their preparation and their use as agents for combating pestsInfo
- Publication number
- CA1115275A CA1115275A CA337,076A CA337076A CA1115275A CA 1115275 A CA1115275 A CA 1115275A CA 337076 A CA337076 A CA 337076A CA 1115275 A CA1115275 A CA 1115275A
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- dihydro
- acid ester
- pyridazin
- oxo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
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- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XUWVIABDWDTJRZ-UHFFFAOYSA-N propan-2-ylazanide Chemical compound CC(C)[NH-] XUWVIABDWDTJRZ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- NQLVQOSNDJXLKG-UHFFFAOYSA-N prosulfocarb Chemical compound CCCN(CCC)C(=O)SCC1=CC=CC=C1 NQLVQOSNDJXLKG-UHFFFAOYSA-N 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
-
- 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
- A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
- A01N57/32—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen 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
- C07F9/6509—Six-membered rings
- C07F9/650905—Six-membered rings having the nitrogen atoms in the positions 1 and 2
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
O-Alkyl-N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amides of the formula
O-Alkyl-N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amides of the formula
Description
5~75 ., .
- 1 - Type Ia The invention relates to certain new N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphos-phoric acid ester-amides, to a process for their preparation and to their use as agents for combating pests, especially as insecticides~ acaricides and nematicides.
It is known that certain S-(1,6-dihydro 6-(thi)oxo-pyridazin-l-yl-methyl)-(thiono)thiol-phosphoric acid ester-amides, for example N-allyl-O-ethyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thionothiolphosphoric acid ester-amide, N,N-dimethyl-O-ethyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-l-yl-methyl)-thiolphosphoric acid ester-amide and N-iso-propyl-O-n-propyl-S-(1,6-dihydro-3-methyl-6-thioxo-pyridazin-l-yl-methyl)-thionothiol-phosphoric acid ester-amide, have insecticidal, acaricidal and nematicidal properties ~see DE~OS (German Published Specification)
- 1 - Type Ia The invention relates to certain new N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphos-phoric acid ester-amides, to a process for their preparation and to their use as agents for combating pests, especially as insecticides~ acaricides and nematicides.
It is known that certain S-(1,6-dihydro 6-(thi)oxo-pyridazin-l-yl-methyl)-(thiono)thiol-phosphoric acid ester-amides, for example N-allyl-O-ethyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thionothiolphosphoric acid ester-amide, N,N-dimethyl-O-ethyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-l-yl-methyl)-thiolphosphoric acid ester-amide and N-iso-propyl-O-n-propyl-S-(1,6-dihydro-3-methyl-6-thioxo-pyridazin-l-yl-methyl)-thionothiol-phosphoric acid ester-amide, have insecticidal, acaricidal and nematicidal properties ~see DE~OS (German Published Specification)
2,34B,736 and 2,603,052). However, the action of these compounds is not always satisractory, especially at low concentrations o~ active compound and when low amounts are used.
The present invention now provides, as new compounds, the N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amides o~ the general ~ormula -CH2_S_p~ R (I) " NH-C3H7-i80 X
25 in which ~.
R represents alkyl with 1 to 6 carbon atoms and .
X represents oxygen or sulphur.
Le A 19 195 \
, . ~ .. .. .
.
, ..
.. - ., . .. ~ ., . ' .
., : . . .
.
The compounds (I) are distinguished by a hi~;h activity as agents for combating pests, in particular by outstanding insecticidal, acaricidal and nematicidal properties.
Preferably, in formula (I), R represents straight-chain alkyl with 1 to 3 carbon atoms and X represents oxygen or sulphur.
The invention also provides a process for the pre-paration of a compound Or the formula (~[), in which a 1,6-dihydro-1-chloromethyl-3-methyl-6-(thi)oxo-pyridazine of the general formula (II), ~-C~12Cl in which X has the meaning stated above, is reacted with a salt of an N-iso-propyl-thiolphosphoric acid ester-amide of the general formula M-S-P ~ (III), 3H7 iso in which R has the meaning stated above and M represents one equivalent of an alkali metal or alkaline earth metal or one ammonium equivalent, if appropriate using a diluentO
Surprisingly, the N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-l-yl-methyl)-thiolphosphoric acid ester-amides (I) according to the invention exhibit a much higher insecticidal, acaricidal and nematicidal action than com-pounds of analogous structure an~ the same type of action which are known from the state of the art.
~ .
Le A 19 195 - : . : - . - , ., . :
.. . . ..
~ ,S~75
The present invention now provides, as new compounds, the N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amides o~ the general ~ormula -CH2_S_p~ R (I) " NH-C3H7-i80 X
25 in which ~.
R represents alkyl with 1 to 6 carbon atoms and .
X represents oxygen or sulphur.
Le A 19 195 \
, . ~ .. .. .
.
, ..
.. - ., . .. ~ ., . ' .
., : . . .
.
The compounds (I) are distinguished by a hi~;h activity as agents for combating pests, in particular by outstanding insecticidal, acaricidal and nematicidal properties.
Preferably, in formula (I), R represents straight-chain alkyl with 1 to 3 carbon atoms and X represents oxygen or sulphur.
The invention also provides a process for the pre-paration of a compound Or the formula (~[), in which a 1,6-dihydro-1-chloromethyl-3-methyl-6-(thi)oxo-pyridazine of the general formula (II), ~-C~12Cl in which X has the meaning stated above, is reacted with a salt of an N-iso-propyl-thiolphosphoric acid ester-amide of the general formula M-S-P ~ (III), 3H7 iso in which R has the meaning stated above and M represents one equivalent of an alkali metal or alkaline earth metal or one ammonium equivalent, if appropriate using a diluentO
Surprisingly, the N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-l-yl-methyl)-thiolphosphoric acid ester-amides (I) according to the invention exhibit a much higher insecticidal, acaricidal and nematicidal action than com-pounds of analogous structure an~ the same type of action which are known from the state of the art.
~ .
Le A 19 195 - : . : - . - , ., . :
.. . . ..
~ ,S~75
- 3 - .:
If, for example, 136-dihydro-l-chloromethyl-3-methyl-6-thioxo-pyridazine and the sodium salt of N-isopropyl-O-methyl thiolphosphoric acid ester-amide are used as starting substances, the reaction of these compounds can be out-lined by the following equation:
~ N + Na-S-P~ 3 -NaCl 1~ N-CH2C 1 --NH-C 3H7- i S o --The formula (II), i.n which X represents oxygen or sulphur, provides a defi.nition of the 1,6-dihydro-1-chloro-methyl-3~methyl-6-(thi)oxo-pyridazines to be used as starting substances. Specifically they are 1,6-dihydro-1-chloromethyl-3-methyl-6-oxo-pyridazine and1,6-dihydro-1-chloromethyl-3-methyl-6-thioxo-pyridazine.
The compounds of the formula (II~ are already known (see DE-OS (German Published Specification) 2,348,736 and 2,603,052).
The formula (III) provides a definition of the salts Or N-iso-propyl-thiolphosphoric acid ester-amides also to be employed as starting substances. Preferably, in this formula, R represents straight chain alkyl with 1 to 3 carbon atoms and M represents sodium or potassium.
Examples which may be mentioned are: the sodi.um salt and potassium salt of O-methyl-N-iso-propyl-thiolphosphoric acid ester-amide, the sodium salt and potassium salt of 0-ethyl-N-iso-propyl-thiolphosphoric acid ester-amide and the sodium salt and potassium salt of O-n-propyl-N-iso-propyl-Le A 19 195 - .
.'. : ' - ': : . ' ' , -: .
~ - , , , ,, . :
~~ -5i;~5
If, for example, 136-dihydro-l-chloromethyl-3-methyl-6-thioxo-pyridazine and the sodium salt of N-isopropyl-O-methyl thiolphosphoric acid ester-amide are used as starting substances, the reaction of these compounds can be out-lined by the following equation:
~ N + Na-S-P~ 3 -NaCl 1~ N-CH2C 1 --NH-C 3H7- i S o --The formula (II), i.n which X represents oxygen or sulphur, provides a defi.nition of the 1,6-dihydro-1-chloro-methyl-3~methyl-6-(thi)oxo-pyridazines to be used as starting substances. Specifically they are 1,6-dihydro-1-chloromethyl-3-methyl-6-oxo-pyridazine and1,6-dihydro-1-chloromethyl-3-methyl-6-thioxo-pyridazine.
The compounds of the formula (II~ are already known (see DE-OS (German Published Specification) 2,348,736 and 2,603,052).
The formula (III) provides a definition of the salts Or N-iso-propyl-thiolphosphoric acid ester-amides also to be employed as starting substances. Preferably, in this formula, R represents straight chain alkyl with 1 to 3 carbon atoms and M represents sodium or potassium.
Examples which may be mentioned are: the sodi.um salt and potassium salt of O-methyl-N-iso-propyl-thiolphosphoric acid ester-amide, the sodium salt and potassium salt of 0-ethyl-N-iso-propyl-thiolphosphoric acid ester-amide and the sodium salt and potassium salt of O-n-propyl-N-iso-propyl-Le A 19 195 - .
.'. : ' - ': : . ' ' , -: .
~ - , , , ,, . :
~~ -5i;~5
- 4 -thiolphosphoric acid ester-amide.
The starting compounds of the formula (III) are new.
These compounds (III) are obtained when N-iso-propyl-thiono-phosphoric acid ester chlorides of the general formula S OR (IV)~
Cl-P
~H C3H7 1 in which R has the meaning stated above (preferably straight-chain alkyl with 1 to 3 carbon atoms), are reacted wi~h at least two equivalents o~ a hydroxy com-pound of the general formula M-OH (V) , in which M has the meaning stated above (preferably sodium or potassium), if appropriate using a diluent, for example water~ methanol or a mixture thereof, at temperatures between 0 and 100C, preferably at 20 to 80C. The reaction products are then obtained, for example, by extraction o~ the mixture with toluene and evaporation of the aqueous phase in vacuo.
The precursors of the formula (IV) are known, or they can be prepared by processes analogous to known processes (see DE-OS (German Published SpeciPication) 2,348,736)~
Examples o~ these precursors which may be mentioned are: O-methyl- 9 O-ethyl- and O-n-propyl-N-iso-propyl-thiono~phosphoric acid ester chloride.
Examples of the hydroxy compounds of the formula (V) whioh may be mentioned are sodium hydroxide and potassium hydroxide.
The process for the preparation o~ the N-iso-propyl-S-(1,6-dihydro-6~(thi)oxo-pyridazin-1-yl-methyl)-thiolphos-phoric acid ester-amides according to the invention is pre~erably carried out using a suitable solvent or diluent.
,.
Le A 19 195 .'"
~ ~ ~ 5 ~ 5
The starting compounds of the formula (III) are new.
These compounds (III) are obtained when N-iso-propyl-thiono-phosphoric acid ester chlorides of the general formula S OR (IV)~
Cl-P
~H C3H7 1 in which R has the meaning stated above (preferably straight-chain alkyl with 1 to 3 carbon atoms), are reacted wi~h at least two equivalents o~ a hydroxy com-pound of the general formula M-OH (V) , in which M has the meaning stated above (preferably sodium or potassium), if appropriate using a diluent, for example water~ methanol or a mixture thereof, at temperatures between 0 and 100C, preferably at 20 to 80C. The reaction products are then obtained, for example, by extraction o~ the mixture with toluene and evaporation of the aqueous phase in vacuo.
The precursors of the formula (IV) are known, or they can be prepared by processes analogous to known processes (see DE-OS (German Published SpeciPication) 2,348,736)~
Examples o~ these precursors which may be mentioned are: O-methyl- 9 O-ethyl- and O-n-propyl-N-iso-propyl-thiono~phosphoric acid ester chloride.
Examples of the hydroxy compounds of the formula (V) whioh may be mentioned are sodium hydroxide and potassium hydroxide.
The process for the preparation o~ the N-iso-propyl-S-(1,6-dihydro-6~(thi)oxo-pyridazin-1-yl-methyl)-thiolphos-phoric acid ester-amides according to the invention is pre~erably carried out using a suitable solvent or diluent.
,.
Le A 19 195 .'"
~ ~ ~ 5 ~ 5
- 5 Possible solvents and diluents are virtually any of the inert organic solvents. These include, as preferences, aliphatic and aromatic, optionally chlorinated hydro-carbons, such as benzine, benzene, toluene, xylene, methylene chloride, chloroform~ carbon tetrachloride, chlorobenzene and o-dichlorobenzene; ethers, such as diethyl ether and dibutyl ether, tetrahydrofuran and dioxan; ~etones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such as aceto-nitrile and propionitrile.
The reaction temperature can be vaxied within a sub-stantial range. In general, the reaction is carried out at from 0 to 100C, preferably at from 20 to 80C.
The process according to the invention is in general carried out under normal pressure.
In general, from 1.0 to 1.2 moles, preferably ~rom 1.05 to 1.15 moles, of the salts tIII) of N-iso-propyl-thiolphosphoric acid ester-amides are employed per mole of the 1,6-dihydro-1-chloromethyl-3-methyl-6-(thi)oxo-pyridazines (II).
The reaction is in general carried out in one of thediluents indicated above and the reaction mixture is stirred at the required temperature for several hours.
Thereafter, it i5 diluted with an organic solvent, for example toluene, and the organic phase is worked up in the customary manner by washing and drying and distilling off the solvent. The refractive index is used for characterising the products, which in general are ob-tained in the form of oils.
As already mentioned~ the new N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amides (I) are distinguished by an outstanding insecticidal, acaricidal and nematicidal activity. They have a good action against sucking and biting insects, and ~5 also against spider mites and nematodes, coupled with a low phytotoxicity.
Le A 19 195 , , ,~ ; , , , , ,: ,. :
. ' . :' ,':'. '., , . , . , ' . ':' ~ ' ,: . :
. . . . . .. .
, . .
~52~5
The reaction temperature can be vaxied within a sub-stantial range. In general, the reaction is carried out at from 0 to 100C, preferably at from 20 to 80C.
The process according to the invention is in general carried out under normal pressure.
In general, from 1.0 to 1.2 moles, preferably ~rom 1.05 to 1.15 moles, of the salts tIII) of N-iso-propyl-thiolphosphoric acid ester-amides are employed per mole of the 1,6-dihydro-1-chloromethyl-3-methyl-6-(thi)oxo-pyridazines (II).
The reaction is in general carried out in one of thediluents indicated above and the reaction mixture is stirred at the required temperature for several hours.
Thereafter, it i5 diluted with an organic solvent, for example toluene, and the organic phase is worked up in the customary manner by washing and drying and distilling off the solvent. The refractive index is used for characterising the products, which in general are ob-tained in the form of oils.
As already mentioned~ the new N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amides (I) are distinguished by an outstanding insecticidal, acaricidal and nematicidal activity. They have a good action against sucking and biting insects, and ~5 also against spider mites and nematodes, coupled with a low phytotoxicity.
Le A 19 195 , , ,~ ; , , , , ,: ,. :
. ' . :' ,':'. '., , . , . , ' . ':' ~ ' ,: . :
. . . . . .. .
, . .
~52~5
- 6 -The compounds (I) according to the invention can thus successfully be employed in plant protection as agents for combating pests.
The active compounds are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, especially insects and acarids, and nematode pests which are encountered in agriculture, in forestry, in the protect-ion of stored products and of materialsv and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of de-velopment. The abovementioned pests include:
from the class of the Isopoda, for example Oniscus asellus, Armadillidium ~ and Porcellio scaber, from the class of the Diplopoda, for example Blaniulus guttulatus;
-from the class of the Ch _opoda, for example Geophilus and ~ spec.;
from the class of the ~ , for example Scuti- ' gerella immaculata;
from the order of -the Thysanura, for example 1episma saccharina; ' ' from the order of the Coll_mbola, for example Onyc_iurus armatus;
from the order of the Orthoptera, for example Blatta orientalis, ~ americana, Leucophaea maderae, Blattella ~ , Acheta domesticus, ~
talpa spp., Locusta migratoria ~ ,' Me'l'an~plus differentialis and'Schi's't'ocerca' ~ ;
_ __ ___ from the order of the'Dermaptera, for example Forficula auricularia; ' from the order of the Isoptera, for example Reticulitermes spp.;
.__ from the order of the ~ , for example '' ~ Va~tatrix, ~ spp. 9' 'Pedlcu'l'us~ h'uman'us Le A 19 195 ', ,, ,, ,, ,, . , - ., , :. ~. ~
, . . : ~ .. , . .. , . .:
, ~ . , , . - : . . , :
~5275
The active compounds are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, especially insects and acarids, and nematode pests which are encountered in agriculture, in forestry, in the protect-ion of stored products and of materialsv and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of de-velopment. The abovementioned pests include:
from the class of the Isopoda, for example Oniscus asellus, Armadillidium ~ and Porcellio scaber, from the class of the Diplopoda, for example Blaniulus guttulatus;
-from the class of the Ch _opoda, for example Geophilus and ~ spec.;
from the class of the ~ , for example Scuti- ' gerella immaculata;
from the order of -the Thysanura, for example 1episma saccharina; ' ' from the order of the Coll_mbola, for example Onyc_iurus armatus;
from the order of the Orthoptera, for example Blatta orientalis, ~ americana, Leucophaea maderae, Blattella ~ , Acheta domesticus, ~
talpa spp., Locusta migratoria ~ ,' Me'l'an~plus differentialis and'Schi's't'ocerca' ~ ;
_ __ ___ from the order of the'Dermaptera, for example Forficula auricularia; ' from the order of the Isoptera, for example Reticulitermes spp.;
.__ from the order of the ~ , for example '' ~ Va~tatrix, ~ spp. 9' 'Pedlcu'l'us~ h'uman'us Le A 19 195 ', ,, ,, ,, ,, . , - ., , :. ~. ~
, . . : ~ .. , . .. , . .:
, ~ . , , . - : . . , :
~5275
- 7 ..
~ , Ha ~ato'pin'us spp. and'Li'n'o'~n'a't'h'us spp.;
from the order of the''Mal'l'o'ph'a~a, for example Trichodectes spp. and Da~al'i'nea spp.;
from the order of the'Thysanoptera, for example Hercinothrips femoral~is and Thrips tabaci;
_. __ __ from the order of the Heteroptera, for example Eury~aster spp.,- Dysde'Fcus i'nt-erme'dius, Piesma' ~ , Cimex lectularius, Rhodnius prolixus and'Tria't'o'ma 5pp.;
from the order of the ~ , for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis ~ E~ Brevico~ brassicae, Cryptomyzus ribis, Doralis fabae, Doralis ~ , Eriosoma lanigerum, Hyalopterus aru dinis, Macrosi~ a~enae, Myzus spp., Phorodon humuli,' ~ padi, Empoasca spp., Euscelis bilobatus, Ne'photettix cincticeps, Lecanium corni, Saissetia oleae, ~ striatellus, Nilaparvata lu~ , Aonidiella aurantii,~'A's'pidiot'us hederae, Pseudococcus spp. and' Ps'ylla spp.;
from the order of the Lepidoptera, for example ' Pectinophora gossypiel'la,' Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hypono'meuta padella, Plutella maculîpennis, Malacosoma'neust'ria,''Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiell_, Phyllocnis_is ~citrella,' ~ spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., ~ eXlgua9 Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,-Trichoplusia ni, ~ pomonell_, Pieris spp., Chilo spp., Pyrausta- nubilalis,~ ~
kuehniella, Gall~e~ria~~~el~l~one~lla, Cac~oe~c~ia po~dana, Capua ~ reticulana~ -h~o~ris~t~on~e~u~ra~ fum ferana~ Clysia mb~i ~e~lla, Homona ~ and Tor'tr'ix' ~iri'dana;
___ ___ from the order of the' Co'leoptera, for example Anobium ~ , ~ do~ini~ca, Hruohidlus - .
' 'obtectus ,' ~..n~O~ ro . obtectus ,' ~ylotrupes ~ , A~ s'tica ~ni,' ~ 'd'eoe~lineEta,'' Le A 19 195 : .
:. :~ .. - . .. . -. . .: . , ., . : : :, :. , .,: . - . - :, : .
-. : . : . -.. : . - . . . .,. . : . :
-
~ , Ha ~ato'pin'us spp. and'Li'n'o'~n'a't'h'us spp.;
from the order of the''Mal'l'o'ph'a~a, for example Trichodectes spp. and Da~al'i'nea spp.;
from the order of the'Thysanoptera, for example Hercinothrips femoral~is and Thrips tabaci;
_. __ __ from the order of the Heteroptera, for example Eury~aster spp.,- Dysde'Fcus i'nt-erme'dius, Piesma' ~ , Cimex lectularius, Rhodnius prolixus and'Tria't'o'ma 5pp.;
from the order of the ~ , for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis ~ E~ Brevico~ brassicae, Cryptomyzus ribis, Doralis fabae, Doralis ~ , Eriosoma lanigerum, Hyalopterus aru dinis, Macrosi~ a~enae, Myzus spp., Phorodon humuli,' ~ padi, Empoasca spp., Euscelis bilobatus, Ne'photettix cincticeps, Lecanium corni, Saissetia oleae, ~ striatellus, Nilaparvata lu~ , Aonidiella aurantii,~'A's'pidiot'us hederae, Pseudococcus spp. and' Ps'ylla spp.;
from the order of the Lepidoptera, for example ' Pectinophora gossypiel'la,' Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hypono'meuta padella, Plutella maculîpennis, Malacosoma'neust'ria,''Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiell_, Phyllocnis_is ~citrella,' ~ spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., ~ eXlgua9 Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,-Trichoplusia ni, ~ pomonell_, Pieris spp., Chilo spp., Pyrausta- nubilalis,~ ~
kuehniella, Gall~e~ria~~~el~l~one~lla, Cac~oe~c~ia po~dana, Capua ~ reticulana~ -h~o~ris~t~on~e~u~ra~ fum ferana~ Clysia mb~i ~e~lla, Homona ~ and Tor'tr'ix' ~iri'dana;
___ ___ from the order of the' Co'leoptera, for example Anobium ~ , ~ do~ini~ca, Hruohidlus - .
' 'obtectus ,' ~..n~O~ ro . obtectus ,' ~ylotrupes ~ , A~ s'tica ~ni,' ~ 'd'eoe~lineEta,'' Le A 19 195 : .
:. :~ .. - . .. . -. . .: . , ., . : : :, :. , .,: . - . - :, : .
-. : . : . -.. : . - . . . .,. . : . :
-
8 ~ S275 c'och'leariae,''Di'abr'ot'i spp.? ~ 'chr'y'so'ce'p'hala, Epilachna ~ari~estis,'At'o'ma~ia spp.g''Ory'zae'phil'us surinamensis, hnthonomus spp.,~Sitophilus spp., Ot~iorrh~_chus sulcatus, Cos'mop'o'lites's'ordi'dus,''Ce'u't'hor'r-hynchus assi~i'Iis,'Hype'ra: p'ost'ica,'D_~me'st'es spp.,''Tr'o'~'o-derma spp., Anthrenus spp., ~ SpF)., ~ spp., Meli~ethes aeneus, 'Ptinus spp.,'Niptus ololeu:cus, Gibbium psylloides, Tribolium spp., Tenebrio 'mo'l'it'or, Agriotes spp. J Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica;
from the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and ~espa spp.;
from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila'melano'ga er~ Musca spp., Fannia spp., Calliphora'erythroce'phala,''Luci'l'ia spp., .. -.
Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxy3 spp., Ces't'rus spp., Hypoderma spp., Tabanus spp., Tann:ia spp., Bibio hort'u'l'anus, Oscinella frit, Phorbia spp., Pegomyia hy'osc'~ami,''Ceratitis capitata, Dacus oleae and Tip a paludosa;
from the order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.;
from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans;
from the order of the Acarina, for example Acarus siro, ~ spp., Ornithodoros spp., Dermanyssus ~ , Eriop~yes ribis, Phyllocopt~uta' oleiVora,''Boop'hiIus spp., ~ spp., Amblyo~ma spp.,''Hy'alo'mma spp.,~Ixodes spp., ~ spp., Cho'rioptes spp.,' Sarc~E~tes spp., Tarsonemus spp.,''Bry'obia''praet'io'sa,''Panonychus spp. and Tetranychus spp..
The plant-parasitic nematodes include ~
spp '~ si'~ilis,''~'~;~, ~ ,::
., .
~ ,~ Hete~lode~ra spp., ~ spp.,~Aph~elen-Le A 19 195 . . , ~ . . - , . , ~ .. ~ . .
. ~ , . ., : ., . :- -. . , . ,:
, .:
- . . ~ . , :
.
:
.
from the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and ~espa spp.;
from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila'melano'ga er~ Musca spp., Fannia spp., Calliphora'erythroce'phala,''Luci'l'ia spp., .. -.
Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxy3 spp., Ces't'rus spp., Hypoderma spp., Tabanus spp., Tann:ia spp., Bibio hort'u'l'anus, Oscinella frit, Phorbia spp., Pegomyia hy'osc'~ami,''Ceratitis capitata, Dacus oleae and Tip a paludosa;
from the order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.;
from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans;
from the order of the Acarina, for example Acarus siro, ~ spp., Ornithodoros spp., Dermanyssus ~ , Eriop~yes ribis, Phyllocopt~uta' oleiVora,''Boop'hiIus spp., ~ spp., Amblyo~ma spp.,''Hy'alo'mma spp.,~Ixodes spp., ~ spp., Cho'rioptes spp.,' Sarc~E~tes spp., Tarsonemus spp.,''Bry'obia''praet'io'sa,''Panonychus spp. and Tetranychus spp..
The plant-parasitic nematodes include ~
spp '~ si'~ilis,''~'~;~, ~ ,::
., .
~ ,~ Hete~lode~ra spp., ~ spp.,~Aph~elen-Le A 19 195 . . , ~ . . - , . , ~ .. ~ . .
. ~ , . ., : ., . :- -. . , . ,:
, .:
- . . ~ . , :
.
:
.
- 9 ~ iZ75 choides spp.,'Lon'gidorus spp., Xiphinema spp., and Trichod~Fus spp..
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions1 powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, sus-pension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols 3 such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl- ~ ' sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant '-liquids which would be gaseous at normal temperature and Le A 19 195 -. : . . . ..
i275 under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals~ such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions1 powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, sus-pension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols 3 such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl- ~ ' sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant '-liquids which would be gaseous at normal temperature and Le A 19 195 -. : . . . ..
i275 under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals~ such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks
10 such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may 15 be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, 20 for example, lignin sulphite waste liquors and methylcellu-lose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and 25 polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs~ azo dyeskuffs or metal phthalocyanine dyestuffs, 30 and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zirlC.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention may :
Le A 19 195 . . .: .
, . ~ , .
L5~75 be used in the form of their formulations of the types that are co~nercially available or in the use forms prepared ~rom these formulations.
The active compound content of the use forms pre-pared from the formulations of the types that are com-mercially available can vary within wide ranges. ~he active compound concentration o~ the use forms can be from 0.0000001 to 100% by weight of active compound, pre~
ferably from 0.01 to 10% by weight.
The compounds may be employed in a customary manner appropriate for the particular use forms.
When used against pests harmful to health and pests of stored products, the active compounds are distinguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.
The present invention also provides an arthropodicidal or nematicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating arthropods (especially insects or acarids~ or nematodes which comprises applying to the arthropods or nematodes, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by arthropods or nematodes by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
Le A 19 195 ` , .
, ~ . ..... .. . .
; . ,, : ,, .; ~ : : :': :. ' ' The pesticidal activity of the compounds of` this invention is illustrated by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given 5 in brackets) of the corresponding preparative Example, which will be found later in this specification.
Example A
Critical concentrakion est/nematodes Test nematode: Meloido~yne incognita Solvent: 3 parts by weight of acetone Emulsirier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of act:ive compound was mixed with the stated amount of solvenl;, the stated amount of emulsifier was added and the concentrate was diluted with water :
to the desired concentr~tion.
The preparation of active compound was intimately mixed with soil which was heavily infested with the test nematodes. The concentration of the active compound in the preparation was of practically no importance; only the amount of active compound per unit volume of soil, which is given hereinafter in ppm (= mg/l~, was decisive.
The treated soil was filled into pots, lettuce was sown in and the pots were kept at a greenhouse temperature of 27 degrees C.
After 4 weeks, the-lettuce roots were examined for infestation with nematodes (root galls), and the degree of effectiveness of the active compound was determined 3 as a percentage. The degree of effectiveness was 100~
when infestation was completely avoided, it was 0% when the infestation was exactly the same as in the case of the control plants in untreated soil which had been infested in the same manner.
:` ~
Le A 19 195 -- . ~ . ~ , . .
: ~ . , .: , .
, .
.
~527S
In this test, for example, the following compounds showed a superior activity compared with the prior art: (1), (2), (3) and (4).
Example B
Phaedon larvae test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Brassica o1eracea) were treated by 15 being dipped into the preparation of the active compound :
and were infested with mustard beetle larvae (~haedon cochleariae), as long as the leaves were still wet.
After the specified periods of time, the degree of destruction was determined in %: 100% meant that all 20 of the beetle larvae had been killed whereas 0% meant .:
that none of the beetle larvae had been killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art: :
(1) 3 (2), (3) and (~).
Example C
Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Bean plants (Phaseolu6 ~ ) which were heavily .
Le A 19 195 ..
.:
, . . ~ , ~ . . . . , , . . . . ~
: : .. : . . , , .. , . ~ . .
. : . ~ ~ . ~, ... . ::: :
. . , . ., . . : . :
~527~;i infested with the two-spotted spider mite '('Te't'r'~n'y'c'h'us urticae) in all stages of development were treated by being dipped into the preparation of the active compound.
After the specified periods of time9 the degree of destruction was determined as a percentage: 100% meant that all of the spider mites were killed whereas 0% meant that none of the spider mites were killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art:
10 (1)~ (2), (3) and (4).
Preparative Exam~les ~: ' ~ ~-CH S-P / 2 5 (1) A mixture of 15.8 g (0.1 mol) of 1,6-dihydro-1-15 chloromethyl-3-methyl-6-oxo-pyridazine and 24.3 g (0.11 mol) of the potassium salt of 0-ethyl-N-iso~propyl-thiol-phosphoric acid ester-amide was heated to 50C in 200 ml of acetonitrile for 13 hours. The reaction mixture was then cooled to 20C and poured into 500 ml of toluene. The toluene solution was washed with 50 ml of saturated sodium bicarbonate solution, dried over sodium sulphate and then evaporated. 25 g (82% of theory) of 0-ethyl-N-iso-propyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiol-phosphoric acid ester-amicle were obtained as a yellow oil 25 with the refractive index n22 : 1.5396.
The following compounds listed were prepared analogously:
N CH2-S-P / 2H5 (2) S - NH-C3~ o -. I.e A 19 195 ' ,' .. .'. .-Yield: 74% of theory; refractive index: n21: 1.6031.
~xample 3 , N ~~ ~ C3H7-,N-CH2-S-P
~ ~ NH-C3H7-iso Yield: 82% of theory; refractive index: n22 : 1.52~0.
~
N-CH2-S~P ~ 3 (4) 3H7 iso Yield: 89% of theory; refractive index n22: 1.5495.
The alkali metal 3alts of the thiolphosphoric acid ester-amides, to be e~ployed as starting materials, could be prepared, for example, as follows:
Example a:
KS p ~,OC~H7 n (5) ~ NH-C3H7-iso A mixture of 150 ml of water, 100 ml of methanol~
61.6 g (1.1 mol) of potassium hydroxide and 107.8 g (0.5 mol) of thionophosphoric acid 0-propyl ester N~isopropyl-amide chloride was boi.led under reflux for 1 hour and then cooled to room temperature. The solution was shaken with 200 ml of toluene and the aqueous phase was separated off and evaporated to dryness in vacuo. The residue was tri-turated with acetone, the insoluble material was filteredoff and the solvent was distilled off from the filtrate in vacuo. 59 g (53% of theory) of the potassium salt of 0-n-propyl-N-iso-propyl-thiolphosphoric acid ester-amide with the melting point 144C remained.
Le A 19 195 :' .. . ,. . ~ .. ~ , , . -. . . : . : ~ - . , :
.. , . ~ . . . . .
- 16 ~ Z75 The following compounds could be prepared analogously:
, OC H
KS-P / 2 5 (6) ~I C3~7 Le ~ 19 195 : . ~ . . . . .
. . ': ' , " ' ' ', .': ., ' . " - ': : ~ ' ' ::' : .
As emulsifying and/or foam-forming agents there may 15 be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, 20 for example, lignin sulphite waste liquors and methylcellu-lose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and 25 polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs~ azo dyeskuffs or metal phthalocyanine dyestuffs, 30 and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zirlC.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention may :
Le A 19 195 . . .: .
, . ~ , .
L5~75 be used in the form of their formulations of the types that are co~nercially available or in the use forms prepared ~rom these formulations.
The active compound content of the use forms pre-pared from the formulations of the types that are com-mercially available can vary within wide ranges. ~he active compound concentration o~ the use forms can be from 0.0000001 to 100% by weight of active compound, pre~
ferably from 0.01 to 10% by weight.
The compounds may be employed in a customary manner appropriate for the particular use forms.
When used against pests harmful to health and pests of stored products, the active compounds are distinguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.
The present invention also provides an arthropodicidal or nematicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating arthropods (especially insects or acarids~ or nematodes which comprises applying to the arthropods or nematodes, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by arthropods or nematodes by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
Le A 19 195 ` , .
, ~ . ..... .. . .
; . ,, : ,, .; ~ : : :': :. ' ' The pesticidal activity of the compounds of` this invention is illustrated by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given 5 in brackets) of the corresponding preparative Example, which will be found later in this specification.
Example A
Critical concentrakion est/nematodes Test nematode: Meloido~yne incognita Solvent: 3 parts by weight of acetone Emulsirier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of act:ive compound was mixed with the stated amount of solvenl;, the stated amount of emulsifier was added and the concentrate was diluted with water :
to the desired concentr~tion.
The preparation of active compound was intimately mixed with soil which was heavily infested with the test nematodes. The concentration of the active compound in the preparation was of practically no importance; only the amount of active compound per unit volume of soil, which is given hereinafter in ppm (= mg/l~, was decisive.
The treated soil was filled into pots, lettuce was sown in and the pots were kept at a greenhouse temperature of 27 degrees C.
After 4 weeks, the-lettuce roots were examined for infestation with nematodes (root galls), and the degree of effectiveness of the active compound was determined 3 as a percentage. The degree of effectiveness was 100~
when infestation was completely avoided, it was 0% when the infestation was exactly the same as in the case of the control plants in untreated soil which had been infested in the same manner.
:` ~
Le A 19 195 -- . ~ . ~ , . .
: ~ . , .: , .
, .
.
~527S
In this test, for example, the following compounds showed a superior activity compared with the prior art: (1), (2), (3) and (4).
Example B
Phaedon larvae test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Brassica o1eracea) were treated by 15 being dipped into the preparation of the active compound :
and were infested with mustard beetle larvae (~haedon cochleariae), as long as the leaves were still wet.
After the specified periods of time, the degree of destruction was determined in %: 100% meant that all 20 of the beetle larvae had been killed whereas 0% meant .:
that none of the beetle larvae had been killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art: :
(1) 3 (2), (3) and (~).
Example C
Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Bean plants (Phaseolu6 ~ ) which were heavily .
Le A 19 195 ..
.:
, . . ~ , ~ . . . . , , . . . . ~
: : .. : . . , , .. , . ~ . .
. : . ~ ~ . ~, ... . ::: :
. . , . ., . . : . :
~527~;i infested with the two-spotted spider mite '('Te't'r'~n'y'c'h'us urticae) in all stages of development were treated by being dipped into the preparation of the active compound.
After the specified periods of time9 the degree of destruction was determined as a percentage: 100% meant that all of the spider mites were killed whereas 0% meant that none of the spider mites were killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art:
10 (1)~ (2), (3) and (4).
Preparative Exam~les ~: ' ~ ~-CH S-P / 2 5 (1) A mixture of 15.8 g (0.1 mol) of 1,6-dihydro-1-15 chloromethyl-3-methyl-6-oxo-pyridazine and 24.3 g (0.11 mol) of the potassium salt of 0-ethyl-N-iso~propyl-thiol-phosphoric acid ester-amide was heated to 50C in 200 ml of acetonitrile for 13 hours. The reaction mixture was then cooled to 20C and poured into 500 ml of toluene. The toluene solution was washed with 50 ml of saturated sodium bicarbonate solution, dried over sodium sulphate and then evaporated. 25 g (82% of theory) of 0-ethyl-N-iso-propyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiol-phosphoric acid ester-amicle were obtained as a yellow oil 25 with the refractive index n22 : 1.5396.
The following compounds listed were prepared analogously:
N CH2-S-P / 2H5 (2) S - NH-C3~ o -. I.e A 19 195 ' ,' .. .'. .-Yield: 74% of theory; refractive index: n21: 1.6031.
~xample 3 , N ~~ ~ C3H7-,N-CH2-S-P
~ ~ NH-C3H7-iso Yield: 82% of theory; refractive index: n22 : 1.52~0.
~
N-CH2-S~P ~ 3 (4) 3H7 iso Yield: 89% of theory; refractive index n22: 1.5495.
The alkali metal 3alts of the thiolphosphoric acid ester-amides, to be e~ployed as starting materials, could be prepared, for example, as follows:
Example a:
KS p ~,OC~H7 n (5) ~ NH-C3H7-iso A mixture of 150 ml of water, 100 ml of methanol~
61.6 g (1.1 mol) of potassium hydroxide and 107.8 g (0.5 mol) of thionophosphoric acid 0-propyl ester N~isopropyl-amide chloride was boi.led under reflux for 1 hour and then cooled to room temperature. The solution was shaken with 200 ml of toluene and the aqueous phase was separated off and evaporated to dryness in vacuo. The residue was tri-turated with acetone, the insoluble material was filteredoff and the solvent was distilled off from the filtrate in vacuo. 59 g (53% of theory) of the potassium salt of 0-n-propyl-N-iso-propyl-thiolphosphoric acid ester-amide with the melting point 144C remained.
Le A 19 195 :' .. . ,. . ~ .. ~ , , . -. . . : . : ~ - . , :
.. , . ~ . . . . .
- 16 ~ Z75 The following compounds could be prepared analogously:
, OC H
KS-P / 2 5 (6) ~I C3~7 Le ~ 19 195 : . ~ . . . . .
. . ': ' , " ' ' ', .': ., ' . " - ': : ~ ' ' ::' : .
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. N-iso-Propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amides of the general formula (I) in which R represents alkyl with 1 to 6 carbon atoms and X represents oxygen or sulphur.
2. Compounds according to claim 1, characterised in that R represents straight-chain alkyl with 1 to 3 carbon atoms and X represents oxygen or sulphur.
3. O-Ethyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide of the formula
4. O-Ethyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-thioxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide of the formula
5. O-n-Propyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide of the formula
6. O-Methyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide of the formula
7. A process for the preparation of an N-iso-propyl-S-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester-amide according to claim 1, characterised in that a 1,6-dihydro-1-chloromethyl-3-methyl-6-(thi) oxo-pyridazine of the general formula (II), in which X has the meaning stated in claim 1, is reacted with a salt of an N-iso-propyl-thiolphosphoric acid ester-amide of the formula (III), in which R has the meaning stated in claim 1 and M represents one equivalent of an alkali metal or alkaline earth metal or one ammonium equivalent.
8. A method of combating arthropods or nematodes which comprises applying to the arthropods or nematodes, or to a habitat thereof, an arthro-podicidally or nematocidally effective amount of a compound according to claim 1.
9. A method according to claim 8 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable diluent or carrier.
10. A method according to claim 9 in which a composition is used con-taining from 0.0000001 to 95% of said compound, by weight.
11. A method according to claim 9 in which a composition is used con-taining from 0.01 to 10% of said compound, by weight.
12. A method according to claim 8, 9 or 11 wherein the compound is O-ethyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide.
13. A method according to claim 8, 9 or 11 wherein the compound is O-ethyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-thioxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide.
14. A method according to claim 8, 9 or 11 wherein the compound is O-n-propyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide.
15. A method according to claim 8, 9 or 11 wherein the compound is O-methyl-N-isopropyl-S-(1,6-dihydro-3-methyl-6-oxo-pyridazin-1-yl-methyl)-thiolphosphoric acid ester amide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2843823.5 | 1978-10-07 | ||
| DE19782843823 DE2843823A1 (en) | 1978-10-07 | 1978-10-07 | N-ISO-PROPYL-S- (1,6-DIHYDRO-6- (THI) OXO- PYRIEZIN (1) -YL-METHYL) -THIOLPHOSPHORSAEURE- ESTERAMIDES, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS A PEST CONTROL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1115275A true CA1115275A (en) | 1981-12-29 |
Family
ID=6051660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA337,076A Expired CA1115275A (en) | 1978-10-07 | 1979-10-05 | N-iso-propyl-s-(1,6-dihydro-6-(thi)oxo-pyridazin-1-yl- methyl)- thiolphosphoric acid ester-amides, a process for their preparation and their use as agents for combating pests |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0010612B1 (en) |
| JP (1) | JPS5553296A (en) |
| AR (1) | AR222352A1 (en) |
| AT (1) | ATE226T1 (en) |
| AU (1) | AU5155979A (en) |
| BR (1) | BR7906435A (en) |
| CA (1) | CA1115275A (en) |
| CS (1) | CS208789B2 (en) |
| DD (1) | DD146242A5 (en) |
| DE (2) | DE2843823A1 (en) |
| DK (1) | DK420479A (en) |
| ES (1) | ES484785A1 (en) |
| IL (1) | IL58392A0 (en) |
| PL (1) | PL119128B1 (en) |
| PT (1) | PT70254A (en) |
| ZA (1) | ZA795331B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2501245Y2 (en) * | 1992-02-04 | 1996-06-12 | 大昭和精機株式会社 | Tool holder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2348736A1 (en) | 1973-09-28 | 1975-04-10 | Bayer Ag | S- SQUARE CLIP ON 1,6-DIHYDROPYRIDAZINE- (1) -YLMETHYL SQUARE CLIP FOR -THIOLPHOSPHORIC ACID ESTER- OR. -ESTERAMIDE DERIVATIVES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS NEMATICIDES |
| DE2603052A1 (en) | 1976-01-28 | 1977-08-04 | Bayer Ag | S- SQUARE CLIP ON 1,6-DIHYDRO- 6-THIOXO-PYRIDAZINE- (1) YLMETHYL SQUARE CLIP FOR - (THIONO) - (DI) -THIOL-PHOPSHOR (PHOSPHON) - ACID ESTER- OR. -ESTERAMIDE DERIVATIVES, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES, ACARICIDES AND NEMATICIDES |
-
1978
- 1978-10-07 DE DE19782843823 patent/DE2843823A1/en not_active Withdrawn
-
1979
- 1979-09-25 AT AT79103633T patent/ATE226T1/en not_active IP Right Cessation
- 1979-09-25 DE DE7979103633T patent/DE2960842D1/en not_active Expired
- 1979-09-25 EP EP79103633A patent/EP0010612B1/en not_active Expired
- 1979-10-01 PT PT70254A patent/PT70254A/en unknown
- 1979-10-04 IL IL58392A patent/IL58392A0/en unknown
- 1979-10-04 DD DD79216031A patent/DD146242A5/en unknown
- 1979-10-05 BR BR7906435A patent/BR7906435A/en unknown
- 1979-10-05 CA CA337,076A patent/CA1115275A/en not_active Expired
- 1979-10-05 ZA ZA00795331A patent/ZA795331B/en unknown
- 1979-10-05 CS CS796799A patent/CS208789B2/en unknown
- 1979-10-05 AR AR278384A patent/AR222352A1/en active
- 1979-10-05 ES ES484785A patent/ES484785A1/en not_active Expired
- 1979-10-05 PL PL1979218751A patent/PL119128B1/en unknown
- 1979-10-05 DK DK420479A patent/DK420479A/en unknown
- 1979-10-06 JP JP12935079A patent/JPS5553296A/en active Pending
- 1979-10-08 AU AU51559/79A patent/AU5155979A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CS208789B2 (en) | 1981-09-15 |
| DK420479A (en) | 1980-04-08 |
| ZA795331B (en) | 1980-10-29 |
| PL218751A1 (en) | 1980-07-28 |
| EP0010612A1 (en) | 1980-05-14 |
| JPS5553296A (en) | 1980-04-18 |
| AU5155979A (en) | 1980-04-17 |
| DE2960842D1 (en) | 1981-12-03 |
| IL58392A0 (en) | 1980-01-31 |
| EP0010612B1 (en) | 1981-09-16 |
| DE2843823A1 (en) | 1980-04-24 |
| DD146242A5 (en) | 1981-02-04 |
| PT70254A (en) | 1979-11-01 |
| PL119128B1 (en) | 1981-11-30 |
| ES484785A1 (en) | 1980-06-16 |
| BR7906435A (en) | 1980-06-17 |
| ATE226T1 (en) | 1981-10-15 |
| AR222352A1 (en) | 1981-05-15 |
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