GB1570537A - Creation of Inventions and Patents with Artificial Intelligence

GB1570537A – Pyridylphosphorus acid derivatives useful as pesticides
– Google Patents

GB1570537A – Pyridylphosphorus acid derivatives useful as pesticides
– Google Patents
Pyridylphosphorus acid derivatives useful as pesticides

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Publication number
GB1570537A

GB1570537A
GB9160/77A
GB916077A
GB1570537A
GB 1570537 A
GB1570537 A
GB 1570537A
GB 9160/77 A
GB9160/77 A
GB 9160/77A
GB 916077 A
GB916077 A
GB 916077A
GB 1570537 A
GB1570537 A
GB 1570537A
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compound
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dimethyl
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1976-03-06
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BASF SE

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BASF SE
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1976-03-06
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1977-03-04
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1980-07-02

1977-03-04
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BASF SE

1980-07-02
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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings

C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members

C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms

C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System

C07F9/02—Phosphorus compounds

C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom

C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom

C07F9/576—Six-membered rings

C07F9/58—Pyridine rings

Description

PATENT SPECIFICATION ( 11) 1570 537
L’ ( 21) Application No 9160/77 ( 22) Filed 4 March 1977 C ( 31) Convention Application No2 609 312 ( 19) ( 32) Filed 6 March 1976 in ( 33) Fed Rep of Germany (DE) ef ( 44) Complete Specification published 2 July 1980 ( 51) INT CL 3 C 07 F 9/58; A 01 N 57/08 ( 52) Index at acceptance C 2 P I Ll 2 E 13 2 E 18 C 2 E 19 B 2 E 24 2 E 25 A 2 L 13 2 L 18 C 2 L 19 G 2 L 25 A 3 B 13 3 B 14 A 3 B 15 A 3 B 18 C 3 B 19 B 3 C 13 3 C 18 C 3 C 19 G 3 C 27 3 C 28 3 C 29 A 3 C 29 B 7 9 Bl B ( 54) NEW PYRIDYLPHOSPHORUS ACID DERIVATIVES USEFUL AS PESTICIDES ( 71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
The present invention relates to new pyridylphosphorus acid derivatives, a 5 process for their manufacture, and pesticides containing these phosphoric acid derivatives as active ingredients.
It is known (German Patent No 1,445,659) that pyridylphosphorus compounds bearing halogen atoms on the pyridyl radical have an insecticidal action However, the persistence of these active ingredients is unsatisfactory for combating for 10 instance flies, fruit flies and caterpillars.
The new pyridylphosphorus acid derivatives of the present invention have the formula I 0 CH R O-C A _ 2 p OR 3 where X denotes hydrogen or halogen, Y denotes oxygen or sulfur, R’ denotes the 15 radical of an alcohol or phenol R’OH, R 2 denotes the radical of an aliphatic hydrocarbon or benzene compound R 2 H or denotes -OR 4 or -SR 4 where R 4 is the radical of an alcohol R 4 OH or thiol R 4 SH or denotes R 5 R 6 N where R 5 R 6 NH is ammonia or a primary or secondary amine, and R 3 denotes the radical of an alcohol R 30 H 20 Preferably R’ denotes linear or branched alkyl, alkenyl or alkynyl of a maximum of 6 carbon atoms, or unsubstituted or halogen-substituted phenyl or benzyl, R 2 denotes linear or branched alkyl, unsubstituted phenyl, substituted phenyl, alkyloxy or alkylthio of a maximum of 6 carbon atoms, alkenyloxy or alkenylthio of a maximum of 6 carbon atoms, alkynyloxy or alkynylthio of a 25 maximum of 6 carbon atoms, amino or alkylamino with from 1 to 4 carbon atoms in the alkyl moiety, or dialkylamino with from 1 to 4 carbon atoms per alkyl moiety, and/or R 3 denotes alkyl of from 1 to 4 carbon atoms.
Examples of radicals R’ are the alkyl groups methyl, ethyl, n-propyl, isopropyl, butyl, pentyl and hexyl, the alkenyl groups allyl, butenyl, pentenyl and hexenyl, the 30 alkynyl groups propargyl, butynyl, isobutynyl, pentynyl and hexynyl, and phenyl, pchlorophenyl, o-chlorophenyl, m-chlorophenyl, 3,4-dichlorophenyl, 3,5dichlorophenyl, 2,4-dichlorophenyl, 2,4,5-trichlorophenyl, benzyl, p-chlorobenzyl, 3,4dichlorobenzyl, and 2,4,5-trichlorobenzyl.
Alkyl groups which R 2 may denote include methyl, ethyl, n-propyl, isopropyl, 35 butyl, pentyl and hexyl; alkyloxy, alkenyloxy and alkynyloxy groups which R 2 may denote include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, hexoxy, propenoxy, butenoxy, hexenoxy, propyn-( 2)-oxy, butynoxy, isobutynoxy, and hexynoxy; alkylthio, alkenylthio and alkynylthio groups which R 2 may denote include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, hexylthio, propenylthio, butenethio, e g, butene-( 2)-thio, hexenethio, propyne-( 2)-thio, butynethio, isobutynethio, pentynethio and hexynethio R 2 may 5 alternatively denote an amine group, an alkylamino group, e g, methylamino, ethylamino, n-propylamino, isopropylamino, tert -butylamino, n-butylamino or sec-butylamino, or a dialkylamino group, e g, dimethylamino, diethylamino, di-npropylamino, diisopropylamino,di-n-butylamino, di-sec-butylamino or methylethylamino 10 Alkyl radicals for R 3 include methyl, ethyl, n-propyl, isopropyl and butyl.
Any halogen, i e fluorine, chlorine, bromine and iodine, may be used for X, chlorine and bromine being preferred.
The pyridylphosphorus acid derivatives of the invention have in general a better insecticidal and acaricidal action than prior art compounds having an 15 analogous constitution and scope of action An outstanding feature is their excellent persistence.
The new phosphorus acid derivatives may be prepared by reaction of 6hydroxy-2,4-dimethylpyridine carboxylic acid esters-( 3) of the formula o CH 3 R 1 o-‘ IN X II 20 CH; N ‘ OH with a phosphorus acid derivative of the formula Y R 2 Hal-P III.
OR 3 The symbols R’, R 2, R 3, X and Y in formulae II and III have the above meanings.
Hal denotes halogen, especially chlorine or bromine.
The reaction is preferably carried out in a solvent or diluent inert to the 25 reactants Particularly suitable examples are ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and diethyl ketone, nitriles such as acetonitrile and propionitrile, chlorinated aliphatic hydrocarbons such as dichloromethane, 1,1-dichloroethane and 1,2-dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylenes and chlorobenzenes, dimethyl 30 formamide and dimethyl sulfoxide.
The hydrogen halide evolved during the reaction may be removed from the mixture by passing in an inert gas, e g, nitrogen, or by binding it with an acid acceptor Any conventional acid-binding agent may be used for this purpose The following compounds are particularly suitable: alkali carbonates, alkali 35 bicarbonates, e g, sodium carbonate, alkali alcoholates, e g, sodium and potassium ethylate and sodium and potassium methylate, aliphatic, aromatic and heterocyclic amines, e g, trimethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine.
40) In some cases, for instance when sterically hindered compounds of formulae II 40 or III are used, it is advisable, in order to increase the conversion, to prepare the alkali metal salts of compounds of formula II first, and then to react them with the phosphorus acid derivatives of the formula III.
The two reactants may be used in equimolar amounts, or either may be used in excess 45 Reaction temperatures are from O to 150 C, preferably 50 to 90 C.
The pyridine derivatives of the formula II used as starting compounds may be obtained in a conventional manner by reaction of isodehydroacetic acid esters of the formula IV with ammonia (Ann Chem, 259, 173-186, 1890):
1,570,537 0 p H 3 0 Cif 3 CH O CH OH 33 IV 11 The substituents R’ and X have the above meanings.
To obtain the pyridine derivatives of the formula II, the isodehydroacetic acid esters of the formula IV may, as is known from the literature, be gassed with ammonia, without a solvent, first at 20 C and then at 150 C to complete the 5 reaction The product obtained may be taken up in methanol and the pyridine derivatives of the formula II precipitated with ether or petroleum ether.
The new compounds of the invention are obtained as oils which usually cannot be distilled without decomposition occurring; however, “incipient distillation”, i e, heating for a fairly long period of time at moderately elevated temperatures 10 and subatmospheric pressure, removes the residual volatiles and enables the compounds to be purified in this way NMR spectra may be used to identify the compounds.
The following preparative examples illustrate the preparation of the new phosphorus acid derivatives In the examples, parts by weight bear the same 15 relation to parts by volume as kilograms to liters.
0 CH 3 1 C 2 H 50 “CN ” % CH 3 O-P ( O C 2115)2 18 parts by weight of sodium methylate ( 30 % by weight solution in methanol) is added to 19 5 parts by weight of 2-hydroxy-4,6-dimethylpyridinecarboxylic acid ethyl ester-( 3) in 150 parts by volume of methanol, and the mixture stirred for 1 20 hour at 60 C The solvent is then removed, the residue is taken up in 100 parts by volume of acetonitrile, and 18 9 parts by weight of diethoxythiophosphoryl chloride is added The mixture is stirred for 5 hours at 70 C and then cooled, the precipitate is filtered off and the filtrate concentrated The oil which remains is taken up in toluene and treated with 2 %o by weight aqueous sodium bicarbonate solution The 25 organic phase is dried over sodium sulfate, concentrated and subjected to incipient distillation at 60 C There is obtained 32 parts by weight ( 92 % of theory) of a pale yellow oil.
C 14 H 22 NP Os S ( 347) C H N P S 30 Calc: 48 5 6 3 4 0 8 9 9 2 Found: 47 8 6 6 4 3 9 3 9 2 M Hz nmr spectrum in CDCI 3 (& values): 1 38 ( 9 H); 232 ( 3 H); 2 5 ( 3 H); 4.15-4 58 ( 6 H): 6 77 ( 1 H).
V i 3 2 e 130O o XJ 35 OH 3 O-P O-C 2 H 5 17.6 parts by weight of phenylthiophosphonic acid ethyl ester chloride is added to 14 5 parts by weight of 2-hydroxy-4,6-dimethylpyridinecarboxylic acid methyl 1,570,537 ester-( 3) in 150 parts by volume of acetonitrile; the mixture is stirred for 6 hours at to 70 C while passing in dry nitrogen The solvent is then removed, the oil which remains is taken up in toluene and treated with 2 % by weight aqueous sodium bicarbonate solution The organic phase is dried over sodium sulfate, filtered and concentrated Incipient distillation at 60 C/0 1 mm Hg gives 24 8 parts 5 by weight ( 85 O of theory) of a pale yellow oil.
C 1-H 20 NPO 45 ( 365) C H N S P Calc: 55 9 5 5 3 8 8 8 8 5 Found: 55 5 5 7 4 0 9 5 9 2 10 M Hz nmr spectrum ( 8 values): 1 3 ( 3 H); 2 18 ( 3 H); 2 43 ( 3 H); 3 8 ( 3 H); 4.05-4 67 ( 2 H): 5 5 ( 1 H); 7 16-7 6 ( 3 H); 7 7-8 2 ( 2 H).
O CH 3 3 @_CH 2-O-C CH 3 O-P( O C 2 H 5)2 10.9 parts by weight of 2-hydroxy-4,6-dimethylpyridinecarboxylic acid benzyl ester-( 3), 10 parts by weight of finely powdered sodium carbonate and 7 35 parts by 15 weight of diethoxythiophosphoryl chloride are stirred for 7 hours at 60 C After the mixture has cooled, the precipitate is filtered off and the filtrate is concentrated.
The residue is stirred with toluene and washed with 2 % by weight aqueous sodium bicarbonate solution The organic phase is dried over sodium sulfate, filtered, concentrated, and subjected to incipient distillation at 60 C/0 1 mm Hg There is 20 obtained 11 7 parts by weight ( 70 % of theory) of a yellow oil.
C 19 H 24 NP Os ( 393) C H N P Calc: 58 0 6 1 3 6 7 9 Found: 57 6 6 6 3 8 7 7 25 220 M Hz nmr spectrum ( 8 values): 1 47 ( 6 H); 2 28 ( 3 H); 2 55 ( 3 H); 4 3-4 55 ( 4 H); 5.5 ( 2 H); 6 92 (IH); 7 38-7 52 ( 5 H).
The following compounds are obtained analogously:
R 10 C H X x y CH N 3-P-R 2 OR 3 1,570,537 No R’ R 2 R 3 X y M Hz nmr spectrum; 3 values CH 3 CH, CH, CH 3 CH 3 C 2 H, C 2 H, C 2 H, CH, CH, CA C 2 H, C 2 H, C^ OCH, H Br H H H cl cl H H cl H H Br H S S S S S S S S S S Mliz: 1 32 ( 6 H); 2 3 0 M 2 46 O M 3 87 Offi; 3.75-4 64 ( 4 M 6 72 (M).
M Hz: 1 28 ( 6 M 2 33 Offi; 2 5 Offi; 3 9 Offi; 3.73 -4 7 3 (M.
M Hz: 1 28 ‘1 49 OW; 2.35 O M 2 52 OM; 4.13-4 61 ( 6 H).
M Hz: 1 15-1 6 ( 9 M 2.28-2 33 ( 6 M 4 2-4 6 ( 6 H).
C’H, C’H, ey, C 2 H 1 C 2 H 1 C 2 H, CH, CH, CH, C 2 H, CH, n-CH 7 C 2 H, CH, 1 2 0 C 2 H, S-i-CH 7 0 C 2111 NHCH, 0 C 2 H, 0 C 2 H, Sn-CH, N Wi CH 7) S-n-CH 7 CH, CH, 0 CH, N(CH), E’, -_j C) Lh -j (J 1 No R’ R 2 R 3 X Y M Hz nmnr spectrum; 8 values 18 c 2 H, S-n-Cff H 7 C 2 H, Br S 60 M Hz: 1 02 ( 3 H); 1 2-1 6 ( 6 H); 1 73 ( 2 H); 2 45 ( 6 11); 2.8-3 3 ( 2 H); 4 33 ( 2 H); 4.44 ( 2 H).
19 C 2 H, S- n-Cff H 7 C 2 H, H S 60 M Hz: 1 00 ( 3 H); 1 17-1 6 ( 6 H); 1 75 ( 2 H); 2 32 ( 3 H); 2.50 ( 3 H); 2 75 ( 3 H); 2 75-3 3 ( 2 H) 4 0-4 5 ( 4 H); 6 83 ( 1 H).
20(j’>-CH 2 0 C 2 H C 25 H S 220 M Hz: 1 48 ( 6 H); 2 43 ( 3 H) 2 57 ( 3 H) 4 37-4 6 ( 4 H); 5 53 ( 2 H); 6 91 (MH); 7.45-7 72 ( 5 H) 21 CH (a C 2 H, H S 220 M Hz: 1 47 ( 3 H); 2 34 “-I ( 3 H);O2 5 ( 3 H); 4 42-4 68 ( 2 H); 4 49 ( 2 H); 6 81 ( 1 H); 7.33-7 82 ( 8 H); 7 96-8 4 ( 2 H).
22 i-CH, 0 C 2 H, C 2 H, H S 23 i-CH, n-CH 7 -S C 2 H, H 0 24 C 2 H, n-CHS CH, H 0 C 2 H, n-C 4 H 9 S CH, cl 0 26 CH 2 =CH-CH 2 OCH, C 2 H 5 H S 27 HCMC-CH 2 n-C 3 HS C 2 H 5 H S 28 W=-C-CH(CH 3) C 2 HS-0 CH, H S ell 29 i-C 3 H 7 NFI-(-CH 7) C 2 H, cl O i-CAH N(CHI) CH 3 H 0 31 i-CAH NHCH 3 C 2 H, Br 0 CL 32 OYCH,0 C 2 H, H S cl 34 Cl N(CH 3)2 C 2 H 5 H 0 ci-tC 11 NH Oi-Cf Hl) CAH H 0 36 CH 3-CH,-CH CH, 0 CAH cl S 37 C 2 H, n-CH 71 n-C 3 H Br S 38 CH 3 n-CH,0 n-CAH cl 0 39 CHI CH, C 2 H, H S CH 3 C 2 H, C 2 H, cl S 41 C 2 H 1 CH 3 CH 3 H S No.
R 2 R 3 X y M Hz nmr spectrum; 5 vt Llues 0 O No R R 2 R 3 X Y MHZ nmr spectrum; S values 42 C 2 Hs C 2 Hs C 2 Hs Br S 43 i-C 3 H 7 CH 3 C 2 Hs H S 44 i-C 3 H 7 CH 3 C 2 Hs H S Applications of the compounds of the invention as pesticides may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering The forms of 5 application depend entirely on the purpose for which the compounds are being used; in any case they should ensure a fine distribution of the active ingredient.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc and oils of vegetable or animal 10 origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc, and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, Nmethyl 15 pyrrolidone, water, etc are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or 20 emulsifiers Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, 25 alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and 30 9 1,570,5379 naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene 5 oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier 10 Granules, e g coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers 15 such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders.
The formulations generally contain from 0 1 to 95, and preferably O 5 to 90, % by weight of active ingredient 20 The active ingredients may also be successfully used in the ultra-low volume method, where it is possible to apply formulations containing more than 95 % of active ingredient.
There may be added to the individual active ingredients (if desired, immediately before use (tankmix)) oils of various types, herbicides, fungicides, 25 insecticides and bactericides.
These, agents may be added to the compounds according to the invention in a ratio by weight of from 1:10 to 10:1.
Formulations of the active ingredients are described in the following formulation examples 30 EXAMPLE A.
parts by weight of O,O-diethyl-O-l 4,6-dimethyl-5-carboethoxypyridin-( 2)yll-thiophosphate is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of 35 dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to I mole of castor oil By pouring the solution into 100, 000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0 02 % by weight of the active ingredient.
EXAMPLE B 40 parts by weight of O,O-diethyl-O-l 4,6-dimethyl-5-carbobenzyloxypyridin( 2)-yll-thiophosphate is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil By pouring the 45 solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0 02 % by weight of the active ingredient.
EXAMPLE C.
20 parts by weight of O,O-diethyl-O-l 4,6-dimethyl-3-bromo-5-carboethoxy 50 pyridin-( 2)-yll-thiophosphate is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 55 0.1 %o by weight of the active ingredient.
EXAMPLE D.
parts by weight of O,O-diethyl-O-l 4,6-dimethyl-5-carbomethoxypyridin-( 2) yll-thiophosphate is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been 60 1,570,537 sprayed onto the surface of this silica gel A formulation of the active ingredient is obtained having good adherence.
The active ingredients according to the invention may be used for combating pests such as sucking and biting insects, Diptera and mites by applying an effective amount of such an active ingredient to the pests or the objects to be protected from 5 pest attack.
The main representatives of the sucking insects are aphids (Aphidae) such as Muzus persicae, Doralis fabae, Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solanifolii, Cryptomyzus korschelti, Sapaphis mali, Hyalopterus arundinis and Myzus cerasi, and bugs such as Piesma quadratum, Dysdercus intermedius, Cimex lectularius, 10 Rhodnius prolixus and Triatoma infestans.
The most important of the biting insects are Lepidoptera such as Plutella maculipennis, Lymantria dispar, Euproctis chrysorrhoea and Malacosoma neustria, further Mamestra brassicae, Agrotis segetum, Pieris brassicae, Hyponomeuta padella, Ephestia ktuhniella and Galleria mellonella 15 Other representatives of biting insects are beetles (Coleoptera) such as Sitophilus granarius, Leptonotarsa decemlineata, Dermestes frischi, Tribolium castaneum, Calandra or Sitophilus zeamais, Stegobium paniceum, Tenebrio molitor, including soil-borne species such as wireworms (Agriotes spec) and cockchafers (Melolontha melolontha); cockroaches such as Blatella germanica, Periplaneta 20 americana, Blatta orientalis, Blaberus giganteus, Blaberusfuscus, and Henschoutedenia flexivitta; Orthoptera, e g, Acheta domestica, termites such as Recticulitermes flavipes, and Hymenoptera such as ants, e g, Lasius niger.
The Diptera essentially encompass flies such as Drosophila melanogaster, Ceratitis capitata, Musca domestica, Fannia canicularis, Phormia regina, Calliphora 25 erythrocephala and Stomoxys calcitrans; mosquitoes such as Aedes aegypti, Culex pipiens and Anopheles stephensi.
Of the mites (Acari) particular importance attaches to spider mites (Tetranychidae) such as Tetranychus telarius (= Tetranychus althaeae or Tetranychus urticae) and Paratetranychus pilosus (= Panonychus ulmi); gall mites, e g, Eriophyes 30 ribis, and Tarsonemidae, e g, Hemitarsonemus latus and tarsonemus pallidus; and finally ticks such as Ornithodorus moubata.
The following use examples demonstrates the biological action of the compounds of the invention The experiments were carried out with certain of the active ingredients identified in the foregoing preparative examples and associated 35 table (the same compound numbers being used); the prior art active ingredient
O,O-diethyl-O-l 3,5,6-trichloropyridyl-( 2)l-thiophosphate was used for comparison purposes.
EXAMPLE 1.
Action on caterpillars of the cabbage moth (Plutella maculipennis) 40 Leaves of young cabbage plants are dipped for 3 seconds in aqueous emulsions of the active ingredients and, after having briefly allowed excess liquid to drip off, are placed on a moist filter paper in a Petri dish 10 caterpillars of the 4th larval stage are then placed on each leaf The action is assessed after 48 hours.
Results: mortality in % 45 Concentration of emulsion 0 2 % 0 1 % 0 05 % 0 02 % 0 01 % Compound no 1 100 100 100 100 80 2 100 50 4 100 100 100 80 3 100 100 80 21 100 100 30 100 100 100 20 1,570,537 EXAMPLE 2.
Contact action on ticks (Ornithodorus moubata) Larvae of the tick Ornithodorus moubata in tea bags are dipped for 5 seconds in emulsions of various concentrations; the bags are then suspended The mortality rate is determined after 48 hours 5 Results: mortality in % Concentration of emulsion 0 1 % O 05 o O 02 o O O 01 Compound no I 100 100 100 80 4 80 100 20 16 100 100 30 EXAMPLE 3.
Contact action on houseflies (Musca domestica); continuous contact io O with treated glass plates 10 Roughened glass plates having a side length of 15 x 15 cm are uniformly treated with acetonic solutions of the active ingredients After the solvent has evaporated, 10 4-day old houseflies under a Petri dish ( 10 cm diameter) are placed on each plate The mortality after 4 hours is taken as a guide.
The experiments are repeated at intervals until the treated plates are no longer 15 effective.
The temperature at which the experiments are carried out is 20 C to 22 C.
The mortality rate with 1 mg of active ingredient no 1 was 100 % after 20 days, compared with 80 ‘ after 7 days in the case of I mg of the prior art comparison compound 20

Claims (1)

WHAT WE CLAIM IS:-
1 A compound of the formula 0 CH 3 R 10 C e Y / R 2 c o p \-_, 3 OR 5 where X denotes hydrogen or halogen, Y denotes oxygen or sulfur, R’ denotes the radicdl of an alcahol or phenol R’OH, R 2 denotes the radical of an aliphatic 25 hydrocarbon or benzene compound R 2 H or denotes -OR 4 or -SR 4 where R 4 is the radical of an alcohol R 4 OH or thiol R 4 SH or denotes R 5 R 6 N where R 5 R 6 NH is ammonia or a primary or secondary amine, and R 3 denotes the radical of an alcohol R 30 H.
2 A compound as claimed in claim I, wherein R 2 denotes linear or branched 30 alkyl, unsubstituted phenyl, substituted phenyl, alkyloxy or alkylthio of a maximum of 6 carbon atoms, alkenyloxy or alkenylthio of a maximum of 6 carbon atoms, alkynyloxy or alkynylthio of a maximum of 6 carbon atoms, amino or alkylamino with from I to 4 carbon atoms in the alkyl moiety, or dialkylamino with from I to 4 carbon atoms per alkyl moiety 35 3 A compound as claimed in claim 2, wherein R’ denotes linear or branched alkyl, alkenyl or alkynyl of a maximum of 6 carbon atoms, or unsubstituted or halogen-substituted phenyl or benzyl.
4 A compound as claimed in claim 3, wherein R 3 denotes alkyl of from 1 to 4 carbon atoms 40 O,O-diethyl-O-l 4,6-dimethyl-5-carboethoxypyridin-( 2)-yll-thiophosphate.
6 O,O-diethyl-O-l 4,6-dimethyl-5-carbomethoxypyridin-( 2)-yllthiophosphate.
7 O,O-diethyl-O-l 4,6-dimethyl-5-carbobenzyloxypyridin-( 2)-yllthiophosphate.
1,570,537 12 1,570,537 12 8 O-ethyl-S-n-propyl-O-l 4,6-dimethyl-5-carboethoxypyridin-( 2)-ylldithiophosphate.
9 A compound as claimed in claim 1 and hereinbefore identified as any of compounds nos 2, 5 to 10 or 12 to 44.
10 A process for producing a compound as claimed in claim 1 wherein a 6 5 hydroxy-2,4-dimethylpyridine-carboxylic acid ester-( 3) of the formula 0 CH 3 R 10-C _ X II, CH 3 N OH where R’ and X have the meanings given in claim 1 or 3, is reacted with a compound of the formula Y R 2 11/ Hal-P III, 10 R 3 where R 2, R 3 and Y have the meanings given in claim 1, 2 or 4 and Hal denotes halogen, in the presence or absence of a diluent at a temperature of from 0 to C.
11 A process as claimed in claim 10, wherein the reaction is carried out in the presence of an acid acceptor 15 12 A process as claimed in claim 10, wherein the hydrogen halide evolved during the reaction is removed from the reaction mixture by passing in an inert gas.
13 Compounds claimed in claim 1 when prepared by a process claimed in any of claims 10 to 12.
14 A pesticide containing as active ingredient a compound as claimed in 20 claim 1.
A process for combating pests, wherein the pests or the objects to be protected from pest attack are treated with an effective amount of a compound as claimed in claim 1.
16 A process as claimed in claim 15, wherein the pests are selected from 25 sucking insects, biting insects, Dipter and mites.
17 A process as claimed in claim 15, wherein the pests are selected from aphids, bugs, lepidoptera, beetles, cockroaches, orthoptera, flies, mosquitoes, spider mites, gall mites and ticks.
J Y & G W JOHNSON, Furnival House, 14-18 High Holborn, London WC 1 V 6 DE.
Chartered Patent Agents, Agents for the Applicants.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1980.
Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

GB9160/77A
1976-03-06
1977-03-04
Pyridylphosphorus acid derivatives useful as pesticides

Expired

GB1570537A
(en)

Applications Claiming Priority (1)

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Priority Date
Filing Date
Title

DE19762609312

DE2609312A1
(en)

1976-03-06
1976-03-06

NEW PYRIDYL-PHOSPHORIC ACID DERIVATIVES

Publications (1)

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GB1570537A
true

GB1570537A
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1980-07-02

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Title
Priority Date
Filing Date

GB9160/77A
Expired

GB1570537A
(en)

1976-03-06
1977-03-04
Pyridylphosphorus acid derivatives useful as pesticides

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US
(1)

US4083971A
(en)

JP
(1)

JPS6034559B2
(en)

AU
(1)

AU507178B2
(en)

BE
(1)

BE852172A
(en)

CA
(1)

CA1101863A
(en)

CH
(1)

CH628063A5
(en)

DE
(1)

DE2609312A1
(en)

FR
(1)

FR2342987A1
(en)

GB
(1)

GB1570537A
(en)

IL
(1)

IL51375A
(en)

IT
(1)

IT1113270B
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NL
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NL7702238A
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JPH06100105B2
(en)

1984-08-08
1994-12-12
日本電装株式会社

Fuel injector

JPS62142831A
(en)

1985-12-18
1987-06-26
Nippon Denso Co Ltd
Fuel injection device for diesel engine

JPS62210257A
(en)

1986-03-11
1987-09-16
Nippon Soken Inc
Injection pressure control unit of fuel injection pump

US7265917B2
(en)

2003-12-23
2007-09-04
Carl Zeiss Smt Ag
Replacement apparatus for an optical element

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NL292088A
(en)

1962-04-30
1900-01-01

DE1670896C3
(en)

1967-07-26
1975-03-13
Bayer Ag, 5090 Leverkusen

Pyridylphosphoric, -phosphonic or -thionophosphoric (-phosphonic) acid esters, processes for their preparation and agents containing them

CH507655A
(en)

1969-03-28
1971-05-31
Agripat Sa

Pesticides

BE755595A
(en)

1969-09-12
1971-02-15
Mitsui Toatsu Chemicals

INSECTICIDE AND ACARICIDE COMPOSITION

BE791519A
(en)

1971-11-19
1973-05-17
Ciba Geigy

ORGANOPHOSPHORUS COMPOUNDS WITH INSECTICIDAL AND ACARICIDAL ACTION

NL7503551A
(en)

1974-04-01
1975-10-03
Dow Chemical Co

PROCESS FOR THE PREPARATION OF SUBSTITUTED PYRIDINE PHOSPHONATES AND PHOSPHONOTHIOATES, AND PHARMACEUTICAL PREPARATIONS CONTAINING THESE COMPONENTS AS ACTIVE COMPONENTS.

1976

1976-03-06
DE
DE19762609312
patent/DE2609312A1/en
not_active
Withdrawn

1977

1977-02-02
IL
IL51375A
patent/IL51375A/en
unknown

1977-02-03
AU
AU21913/77A
patent/AU507178B2/en
not_active
Expired

1977-02-07
US
US05/765,930
patent/US4083971A/en
not_active
Expired – Lifetime

1977-02-23
CA
CA272,433A
patent/CA1101863A/en
not_active
Expired

1977-02-28
IT
IT48243/77A
patent/IT1113270B/en
active

1977-03-02
NL
NL7702238A
patent/NL7702238A/en
not_active
Application Discontinuation

1977-03-03
JP
JP52022260A
patent/JPS6034559B2/en
not_active
Expired

1977-03-03
CH
CH266877A
patent/CH628063A5/en
not_active
IP Right Cessation

1977-03-04
FR
FR7706509A
patent/FR2342987A1/en
active
Granted

1977-03-04
GB
GB9160/77A
patent/GB1570537A/en
not_active
Expired

1977-03-07
BE
BE175544A
patent/BE852172A/en
not_active
IP Right Cessation

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Publication date

NL7702238A
(en)

1977-09-08

IL51375A0
(en)

1977-04-29

DE2609312A1
(en)

1977-09-15

AU2191377A
(en)

1978-08-10

US4083971A
(en)

1978-04-11

JPS52108977A
(en)

1977-09-12

JPS6034559B2
(en)

1985-08-09

AU507178B2
(en)

1980-02-07

FR2342987B1
(en)

1980-08-01

FR2342987A1
(en)

1977-09-30

IL51375A
(en)

1980-06-30

IT1113270B
(en)

1986-01-20

CA1101863A
(en)

1981-05-26

CH628063A5
(en)

1982-02-15

BE852172A
(en)

1977-09-07

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