CS199506B2 - Insecticide,acaricide and nematocide and process for preparing effective compounds - Google Patents

Abstract

Phosphorus acid ester amides of formula (I) are new (where R and R1 are H, alkyl opt. substd. by halo; or CN; or R and R1 together with the attached N atom form a heterocyclic ring opt. interrupted by other heteroatoms; R2 is the group -NRR1, alkoxy, haloalkoxy or alkyl; hal is Cl or Br; X is O or S). (I) are insecticides, acaricides and nematocides with low toxicity to man and animals. A typical cpd., O-(1-fluoro-2-chloroethyl) phosphoro-dimorpholide, was prepd. in 70% yield by reaction of morpholine with O-(1-fluoro-2-chloroethyl) phosporo-dichloride in benzene.

Description

The present invention relates to novel O- (1-fluoro-2-halo-ethyl) -thiophosphoric (phosphonic acid) phosphonides (phosphonic acids having insecticidal, acaricidal and nematicidal properties), and to a process for the preparation thereof.

It is already known that chloro-substituted phosphoric (phosphonic) alkyl esters such as O, O-diethyl-O- (1,2-dichloroethyl) phosphoric acid ester and O, O-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate are characterized by insecticidal and acaricidal activity (see U.S. Pat. Nos. 2,701,225, 2,947,773 and 3,453,348).

It has now been found that the novel O- (1-fluoro-2-halo-ethyl) -esteramides (phosphoric)

R \

N X / \ ll

R1 p_Q_cHF — Nг — Hal (I), /

Where R ² is

R ¹ and R ¹ are each independently hydrogen or straight or branched (C 1 -C 4) alkyl, or both together with the nitrogen atom to which they are attached form a morpholine or piperidine ring,

R ² radical of the formula

R /, —N, \

R ( ^{1) is a} straight or branched (C 1 -C 4) alkoxy group or an alkyl group having 1 or 2 carbon atoms,

Hal chlorine or bromine and

X oxygen or sulfur have strong insecticidal, acaricidal and nematicidal properties.

It has further been found that O- (1-fluoro-2-haloethyl) (thiono) phosphoric (phosphonic acid) phosphoric acid (phosphonic acids) of the above formula (I) is obtained by reacting compounds of formula (II)

Hal ¹ X \ ll

P — O — CHF — CH2 — Hal (II), /

R3 where

Hal and X are as defined above,

Hal ¹ represents a halogen atom, preferably chlorine and

R ³ represents the radical R ² or Hal ¹ as defined above, reacted with an amine of formula III

R /

NH (III), \

Ri where

R 1 and R 1 are as defined above, optionally in the presence of an acid acceptor and optionally in the presence of a solvent, for the preparation of compounds of formula I wherein R 2 is an alkoxy group as defined above. X is O and R, R 1 and Hal are as defined above, the reaction product of a compound of formula II wherein R ³ is Halo X is O and Hal and Hal are as defined above with an amine of formula III with an alkanol corresponding to the radical R ^2, optionally as alkali metal or alkaline earth metal, or in the presence of an acid acceptor and optionally in the presence of a solvent.

Surprisingly, the O- (1-fluoro-2-haloethyl) ester amides (thiono), phosphoric acids (phosphinic acids of the invention have a better insecticidal, acaricidal and nematicidal effect than the corresponding chloro-substituted phosphoric (phosphonic) alkyl esters of the same constitution The compounds according to the invention thus represent a true enrichment of the prior art. »

If, for example, O- (1-fluoro-2-chloroethyl) ester thionoethane phosphonic acid and diethylamine or O- (1-fluoro-2-chloroethyl) ester, thionophosphoric acid and morpholine or O- methyllCO (1-fluoro-2-chloroethyl) diester phosphoric acid chloride and methylamine or O- (1-fluoro-2-chloroethyl) phosphoric acid dichloride, methylamine and ethanol may be described by the following reaction schemes:

-2) (S¾ SP-O-CHF-CH; Cl «W ¹ .

afcceptor

-2 HCl ^« cQО-СНР-СНдСЬ ^! acid acceptor.

~ HCl »

V ', c)' ^{1 CH 3 Osp} sp-O-CHF ^; CH 2 Cl + CH-NH 2 CH ₂ ^Cl 2

---- »° ^ PO1-CHF-CfaCt

CH ^H * ^d) EN \ O

J> -0-CHF-CH ^- Cl + HJN-CH.

^Ql ' ^z ' ^per

ČHjNH 9

J fp ~ O-CHFCHCl2.

Detection of HCl

DCjHfOH ·

2) acne acceptor

The amines of the formula III and the alcohols corresponding to the radical R @ ² used as starting materials are known and can be prepared in conventional manner and also on an industrial scale.

Examples of such starting materials are:

ammonia, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, N-methylpropylamine, piperidine and morpholine, as well as monomethyl-, -ethyl-,

n-propyl- or -isopropylamine, n-butyl-, sec-butyl-, tert-butyl and isobutylamine, and methanol, ethanol, n- and isopropanol.

• As other starting materials used

Phosphonic acid O- (1-fluoro-2-haloethyl) ester halides,

Phosphoric acid O- (1-fluoro-2-haloethyl) ester dihalide a

O-alkyl-O- (1-fluoro-2-haloethyl) diesterhalides of phosphoric acid are novel and can be prepared in a manner not known in the art by reacting a phosphorous (phosphonic) ester and a vinyl fluoride while treatment with halogenating agents such as chlorine or bromine at a temperature between -50 ° C and + 120 ° C, optionally in the presence of a Friedel-Crafts catalyst and optionally in the presence of a solvent, to give the corresponding O- (1-fluoro-2- halophenethyl) phosphorus (phosphonic) acid halides according to the following reaction scheme:

where

D ^E 9 + CHff-CH-t Wf.

> ^ 'i> ^o ^ OC ^ HI HFC-H »l. ··

Haf. . '. .....

As examples

Hal and Halí are as defined above,

R ⁵ represents an alkyl or alkoxy group as defined above or the radical Hal ¹ ·. and

R 0 represents an alkyl group.

Phosphonic acid O- (1-fluoro-2-haloethyl) ester halides,

Phosphoric acid O- (1-fluoro-2-haloethyl) ester dihalides a

O-alkyl-O- (1-fluoro-2-halogenethyl) phosphoric acid diesterhalides are given by:

Methane- and ethanephosphonic acid O- (2-chloro-1-fluoroethyl) ester chloride,

Phosphoric acid O- (2-chloro-1-fluoroethyl) ester dichloride, hereinafter

Phosphoric acid O- (2-bromo-1-fluoroethyl) ester dichloride,

O-methyl-, Ο-ethyl-, O-n-propyl-, optionally O-isopropyl-O- (2-chloro-1-fluoroethyl) diester, phosphoric acid, and

Phosphoric acid Ο-methyl- or O-ethyl-O- (2-bromo-1-fluoroethyl) diester chloride.

As further starting materials, the O- (1-fluoro-2-haloethyl) ester thiophosphoric acid ester dihalide used, or the O- (1-fluoro-2-haloethyl) ester thiophosphoric acid ester monohalide, can be prepared from the corresponding

Of β-compounds

II o

and alkane- or aryldithiophosphonic anhydrides, optionally in admixture with phosphorous sulfochloride and optionally in the presence of a solvent, according to the following reaction scheme:

where

K a and H a are as defined above, and H a is a C 1 - or C 2 alkyl group

R ⁵ represents an alkyl or aryl group.

Examples of O- (1-fluoro-2-chloroethyl) -thiophosphoric acid ester dihalides or of the O- (1-fluoro-2-chloroethyl) thionophosphonic acid monohalides are as follows: O- (2-chloro-1-fluoroethyl) ester chloride and thionophosphoric acid O- (2-chloro-1-fluoroethyl) ester dichloride.

O- (1-fluoro-2-haloethyl) -O-alkyldiesterhalides of thionophosphoric acid, used as additional starting materials, are new, but can be prepared in a manner known per se from O- (1-fluoro-2-haloethyl) thionophosphoric acid ester dihalides and alcohols.

Examples which may be mentioned are: O-methyl, O-ethyl, O-n-propyl- and O-sopropyl-O- (2-chloo-11-fluoroethyl) di-thionophosphoric acid chloride.

The process for the preparation of the active compounds according to the invention is preferably carried out using suitable solvents and diluents. Suitable solvents and diluents which may be mentioned are virtually all inert organic solvents, in particular aliphatic and aromatic or chlorinated hydrocarbons, such as benzene, toluene, xylene, petrol, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, esters, e.g. diethyl ether, dibutyl ether and dioxane, ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, and in addition nitriles such as acetonitrile.

All the usual acid-binding agents can be used as acid acceptors. Alkali metal carbonates such as sodium carbonate and potassium carbonate, and furthermore aliphatic, aromatic or heterocyclic amines, such as triethylamine, trimethylamine, dimethylaniline, dimethylbenzylanimine and pyridine, have proved to be particularly suitable. An excess of the starting amine may also serve as the acid acceptor.

The reaction temperature can be varied within a wide range. In general, the reaction is carried out at a temperature between 0 and 100 ° C, preferably at -20 to 40 ° C.

The reaction of the invention is generally carried out under normal pressure. »

Working in the sense of the reaction scheme

a) the reactants are preferably used in an equimolar ratio. Excess of any of the reaction components has no significant advantages. The reaction is preferably carried out in one of the solvents mentioned above in the presence of an acid acceptor. The reaction mixture is worked up in the usual manner by filtration, washing the filtrate and distilling off the solvent.

Working in accordance with the reaction scheme

b) the phosphoric acid dihalide and the amine are used in a molar ratio of 1: 2 and the reaction is carried out as described above.

Working in terms of reaction schemes

c) and d), the reactants are also used in an equimolar ratio and the reaction mixture is worked up as described above.

The novel compounds of the formula I result in part in crystalline form and are characterized by their sharp melting points. Liquid products have constant boiling points. Some of the new compounds are obtained in the form of oils which cannot be distilled without decomposition, but can be purified by so-called "distillation", ie by longer heating under reduced pressure to moderate elevated temperature, which removes the last residual volatiles. Refractive index is used to characterize these compounds.

As mentioned above, the O- (1-fluoro-2-haloethyl) ester amides (thiono phosphoric acids) of the present invention have excellent insecticidal, acaricidal and nematicidal activity. and against pests of stocks and exhibit good activity against both absorbent and voracious insects and mites at relatively low phytotoxicity.

For this reason, the compounds according to the invention can be successfully used as agents for pest control in plant protection as well as in hygiene and stock protection.

The active compounds according to the invention have good plant compatibility and favorable warm-blood toxicity and are suitable for controlling pests, in particular insects, spider mites and nematodes in agriculture, forestry, in the protection of material stocks, as well as in the field of hygiene. They are effective against normally susceptible and resistant species as well as against all or only individual stages of development of pests. The above mentioned pests include:

from the order of the Isopoda, for example Onicsuc asellus, Armadillidium vulgare, Porcellio scaber;

from the class of the millipedes (Diplopoda), for example, the blind millipede (Blaníulus guttulatus);

from the class of the Chilopoda, for example Geophilus carpophagus, Scutigera spec.

from the centipede class (Symphyla), for example

Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharlna;

from the order of the Collembola, for example Onychíurus armatus;

from the order of the Orthoptera, such as the cockroach (Blatta orientalis), the cockroach (Periplaneta americana), Leucophaea maderae, the Russian cockroach (Blattella germanica), the cricket (Acheta domesticus), the mole cricket (Gryllotalpa spec.), Locusta migratorloides),

Melanoplus differentialis, Schistocerco gregaria from the order of the Dermaptera, for example the earwig (Forficula auricularia);

from the order of the Isoptera, for example Reticulitermes spec.

from the order of the lice (Anoplura), for example: nun (Phylloxera vastatrix), vermin (Pemphigus spec.), your wardrobe (Pediculus humanus corporis), Haematopinus spec ,, Linognathus spec .;

from the order of the Mallophaga, for example, Trichodectes spec., Damalinea spec .;

from the order of the Thysanoptera, for example, Hercinothrips fe moralis, Thrips tabaci;

from the order of the Heteroptera, for example Eurygaster spec.) Dysdercus intermedlus, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Tria torna spec .;

from the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vapo- rariorum, Aphis gossypii, Brevicoryne brassicae, Currant aphid, Cyptic aphid poppy (Doralis fabae),. Apple aphid (Doralis pomi), blood vetch (Erisoma lanigerum), aphid (Hyalopterus arundlnis), Macrosiphum avenae,

Myzus spec., Aphids (Phorodon humuli), Aphids (Rhopalosiphum padi), Empoasca spec., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleari, Laluselph

Nilaparvata lugens, Aonidiella aurantii, Aspldiotusjhederae, Pseudococcus spec., Psylla spec.

from the order of the butterflies (Lepidoptera), for example

Pectinophora gossypiella, Dark-spot Carpet (Bupaluš piniarius), Cheimatobia brumata, Apple-leaved Keyhole (Lithocolletis blancardella), Apple Moth (Hyponomeuta padella), Common Forget-me-not (Plutella maculipennis), Red-eared Chestnut (Malacos pteralis).

Bucculatrix thurberiella, Lymantria spec. leaf tree. (Phyllocnistis citrella), Agrotis spec., Euxoa spec.

Feltia spec.,

Earias insulana, Heliothis spec., Laphygma exigua, Mamestra brassicae, Phanolis flammea, Prodenia litura, Spodoptera spec., Trichoplusia ni, Carpocapsa pomonella, Píeris spec. ,

Chilo spec., Maize moth (Pyrausta nubilalis), Meal moth (Ephestia kuhniella), Wax moth (Gallaria mellonella), Carpet moth (Casoecia podana),

Capua reticulana,

Choristoneura fumiferana,

Clysia ambiguella, Homona · magnanima, Tortrix viridana; from the order of the beetles (Coleopt: era), for example, Anobíum punctatum, Rhizopertha dominica, Bruchidius obtectus. (Acanthoscelides obtectus), Beetle (Hylotrupes bajulus), Alderwort (Agelastica alni), Colorado potato beetle (Leptinotarsa decemlineata), leaf beetle (Phaedon cochleariae),

Diabrotica spec., Psylliodes chrysocephala,

Epilachna varivestis, Atomaria spec., Oryzaepihilus surinamensis, Antonomus spec., Sitophilus spec., Otiorrihynchus sulcatus,

CosiTiopolltes sordidus, Ceuthorrhynchus assimilis,

Hypera, Dermestes spec.

Trogoderma spec., * Anthragus spec., Attagenus spec., Lyctus spec., Meligethes aeneus., Ptinus spec., Niptus hololeucus.

Gibbium psylloides, darkling beetle (Tribolium spec.), Darkling beetle (Tenebrio molitor), blacksmith (Agriotes spec.),

Conoderus spec., Common Cockchafer (Melolontha melolontha), Summer Chafer (Amphimallon solstitialls), Costelytra. zealandica; ..

from the order of the Hymenoptera, for example Diprion spec., Hoplocampa spec., Lasius spec., Monomorlum pharaonis, Hornet (Vespa spec.);

of the order Diptera, for example, the mosquito (Aedes spec.), anofeles (Anopheles spec.), mosquito (Culex spec.), fruit fly (Drosophila melanogaster) ,.

fly (Musea spec.), »sunflower (Fannia spec.), buzzer (Calliphora eryt.hrocephala), buzzer (Lucilia 'spec.),«

Chrysomyia spec.,

Cuterebra spec., Gastrophilus spec.

Hyppobosca spec., Thistle (Stomoxys spec.), Hamster (Oestrus spec.), Hamster (Hypoderma spec.], Horsefly (Tabanus. Spec.),

Tannia spec., Garden Fly (Bibio hortulanus);

Osclnella frit],

Phorbia. spec., Beetweed (Pegomyia hyoscyami), Common Propeller (Ceratitis capitata),

Dacus oleae, 'Tipula paludosa'; from the order of the Siphonaptera, for example, the flea (XenopSylla Cheopis), flea (Ceratophyllus spec.);

from the order of Arachnida, for example

Scorpio maurus,. weaver (Latrodectus · mactans); from the order of the mites (Acarina), for example Acarius sulfur, Argas spec.,

Ornithodoros spec ^, Bumblebee (Dermanyssus gallinae). currant (Eriophyes ribis), Phyllocoptruta oleivora,> · tick (Boophllus spec.), drinker (Rhlpicephalus spec.), drinker (Amblyomma · spec.),

Hyaloma spec., Ixodes spec., Psoroptes spec.

scab (Chorioptes spec. '), Sarcoptes spec.,.

mites (Tarsonemus spec.), red spider mite (Bryobia praetiosa), spider mite (Panonychus spec.), spider mite (Tetranychus spec.).

Water-damaging nematodes include:

(Pratylenchus spec.), Radopholus similis, Dityleňchus dipsaci ,. Tylenchulus semipenetrans, Heterodera spec., Meloidogyne spec., Aphelenchoides spec., Longidorus spec., Xiphinema spec., Trichodorus spec.,

The active compounds according to the invention can be used in the form of commercial preparations and / or in dosage forms prepared from these preparations.

The content of active ingredient in dosage forms prepared from commercial preparations can be varied within wide limits. The concentration of the active ingredient in the dosage forms can range from 0.0000001 to 100% by weight, preferably from 0.01 to 10% by weight.

The application is carried out in a conventional manner adapted to the application form used.

When used against pests in the field of hygiene and against storage pests, the active compounds according to the invention are distinguished by an excellent residual effect on wood and clay and good stability to alkali on lime substrates.

The active ingredients can be converted into obical formulations, such as. solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension-based concentrates, and emulsions, seed dressing powders, natural and synthetic substances impregnated with active substances, small particles coated with polymeric substances and coatings for seed, further for compositions with flammable additives, such as smoke cartridges, smoke smokes, smoke sprays. as well as compositions in the form of concentrates of the active substance for cold fog or hot fog. ;

These compositions are prepared in a simple manner, for example by mixing the active ingredient with fillers, i.e., liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants. and / or crosslinking agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are:. aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes chlorethylated or methylene chloride aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. By liquefied gaseous fillers or carriers is meant liquids which are gaseous at normal temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as. butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of · granulates · are crushed and fractionated natural stone materials such as · limestone, · marble, · pumice, sepiolite and dolomite, as well as synthetic · granules · from inorganic and · organic flours and granules from organic material such as sawdust, coconut shells, corn sticks and tobacco stems. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g. .

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex yellow polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments such as iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active ingredient.

Example A

Limit concentration test (soil insects) experimental insects: Tenebrio molitor - soil larvae solvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

The active ingredient is thoroughly mixed with the soil. The concentration of the active ingredient in the composition plays practically no role, only the amount of active ingredient per unit volume of soil, which is given in ppm (mg / liter), is critical. The treated soil is filled with flower pots and left to stand at room temperature after filling. After 24 hours, the test insects are transferred to the treated soil and after a further 2 to 7 days the percentage of action of the active compound is determined by counting the dead and living specimens of the test insects. When all specimens are killed, the efficacy is 100%, 0% means that the number of live insect specimens is the same as in the control experiment.

The active substances, the amounts of active substances used and the results obtained are given in Table A below:

Table A

Limit test - Tenebrio molitor larvae in soil active substance mortality in% at active substance concentration 20 ppm

О OC2H5

II /

Cl — CH2 — CH — O — Po

Ί \

ClOC2H5 (known)

O — CHF — CHaCl /

G2H5 — P100 \

NH2

O O — CHF — CH2 — Cl

II /

CH3-CH2 — СНг — O — P 100 \

NHC 3 H 7 -ISO

II /

CH2-CH2-CH2-CH2-O-P

O O — CHF — CH2 — Cl

100 ALIGN!

NCH 3 H 7 -ISO ¹⁷

Example Β

Limit concentration / systemic effect test (active substance rooted) experimental insects:. Creme beetle (Phaedon cochleariae) solvent: 3 parts by weight of acetone part by weight of alkyl aryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active agent is thoroughly mixed with the soil. The concentration of the active substance in the composition plays practically no role, only the consumption of active substance per unit volume of soil, which is given in ppm (-mg / liter), is decisive. The treated soil is filled with 18 pots in which cabbage (Brassica oleracea) is planted. The active substance is taken up by the roots of the plants from the soil and transported to the leaves.

After 7 days, only the leaves of the test plants were shown to show a systemic effect on root take. occupy the aforementioned experimental insects. After an additional 2 days, the experiment is evaluated by counting or estimating the number of dead specimens of the test insects. The systemic effect of the test compounds on their root uptake is derived from the observed mortality values. 100% effect means that. all specimens of the test insect were killed, and a value of 0% means that the same number of test insects survived as in the control experiment with untreated soil.

The active substances, the active substance consumption and the results obtained are given in Table B below:

Table B limiting concentration / systemic effect test. (active substance taken over by roots) (larvae of Phaedon cochleariae) active substance mortality in ·%. at the active compound concentration

20. ppmO _0C 2 _Hs : w /

C1-CH2-CH-O-POI

Cl 'OC2H5.

(known)

F

O O — CH — CH2 — Cl

W / '

C 50 H 50 O-P 100

NH — C5H7-1ŠO ·

F

AND

O O — CH — CHaCl 'w / ·

CíHsOo-P100 \

N (C2 H5) 2 .F

AND

O O — CH — CH2Cl

II /,

C2H5-P100

NH2 mortality in% at active substance concentration ppm active substance

F 'I

O O — CH — CH2 — Cl

II /

СНз — CH2 — CH2 — O — P

X

NHC 3 H 7 -ISO

100 ALIGN!

F 1 1 O OCH — CH2 — Cl II / СНз — CH2 — CH2 — CH2 — O — P 100 ALIGN! and NHC 3 H 7 -ISO F СНз 0 0 — CH — CH2 — Cl \ II / CH — O — P / X C2H5 NHC3H7-ISO 100 ALIGN! F Cl — CH2 — CH — O s X / P / X СНзО NH2 , 100

Example C

Limit concentration test experimental nematode: nematode nematode Meloidogyne incognita solvent: 3 parts by weight acetone emulsifier: 1 part by weight alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

The active agent is thoroughly mixed with soil heavily contaminated with test nematodes. The concentration of the active ingredient in the composition plays practically no role, only the amount of active ingredient per unit volume of soil, which is given in ppm, is decisive. The treated soil is filled with pots, the salad is sewn into the soil and the pots are kept in a greenhouse at 27 ° C.

After 4 weeks, nematode lettuce root infestation was determined and the effect of the active compound evaluated in%. The effect is 100% if infestation is completely prevented and 0% if infestation is exactly as high as for control plants growing in untreated but contaminated soil.

Active substances, amounts of active substances used and results obtained The following table C shows:

Table C limit test (Meloidogyne incognita) active substance ..... ..... mortality-% at active substance concentration ppm

O OC2H5  WW C1-CH2-CH-O-P 1 \ ' 0 - I X. ClOC2H5. (known) 1 F O-CH-CH 2 Cl W / .C? H? O — P . NHC 3 H 7 -ISO 100 ALIGN! . F O-CH-CH 2 Cl . IL // C2HOO — P - \ N (-C 2 H 5) 2 100 ALIGN! F \ O-CH-CH 2 Cl WW C2H50-P 100 ALIGN! X. NH2 0 0 — CHF — CH2Cl  · II / · · C2fco-P \ < 100 ALIGN! X N (C2 H0) 2 * 0 0 — CHF — CH2Cl / C2H5-P  \ ' 100 ALIGN! X N (C 2 H 5) 2. F · 1 O-CH-CH2-Cl W / CH3-CH2-CH2-O-P 100 ALIGN! X NHC 3 H 7 -ISO F 1 O - CH - CH 2 - Cl, W / CH 3 - CH 2 - CH 2 - CF 12 - O - P 100 ALIGN!

X

NHC3H7-ISO active ingredient mortality in% at active ingredient concentration ppm ~ S 'NH — C3H7-ISO' '11 /

GI — CH2 — CH — Q — P100 \

NH — C3H7-1SS

F

CI — CH2 — CH — O S100

XiII · P / X

CH3O NH2

Appendix D

Test for peach aphid (Myzus persicae) - contact effect solvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

The prepared active agent is:. sprouts of cabbage (Brassica oleracea), heavily infested with peach aphids (Myzus persicae), are sprayed until dew ..

After a period of time below, mortality was found in%. 100% means that all aphids have been killed, 0% means that no aphids have been killed.

The active substances, the concentration of the active substances, the evaluation time and the results obtained are given in Table D below:

active substance

Table D test on. aphid (Myzus) '- contact effect concentration mortality in% of active substance after 1 day in%

O

II (CH5S) 2P-CH-CCl3 0.1

I 0,01

OH (known)

0

OCHF-CH2-Cl

1 / ·

CH3O — P0.1

X .0,01

NH2

O SCHF-CH2-Cl

1 /

C2H5-P0.1

X0.01

NH2

O SCHF-CH2-Cl

1 /

C2H5O-P 0.1

X 0.01

NH — C 3 H 7 -ISO

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 active substance concentration of the active substance in% mortality in% after 1 day

CH 3 OCHF-CH 2 -C 1 \ 1 / CH — O — P / \ C2H5 NH — C3H7-1SO 0.1 0.01 O OCHF-CH2-Cl II // n-Cu-H-O-P \ NH — C3H7-1SO 0.1 0.01 O OCHF-CH2-Cl 1 / n-CHfr-O-P \ of NH — C3H7-1SO 0.1 0.01 O-OCHF-CH2-Cl 1 / C2H5O-P \ ' N (CH 3) 2 0.1 0.01 O OCHF-CH2-C1 , 1 / C2H5O-P \ N (C 2 H 5) 2 0.1 0.01 About OCHF-CUfCl 0.1 0.01 - q ^ CH ^ OCHF-Cl ^C 2 ^H s' ^P ^ I ^ O 0.1 0.01

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

Example E

Test for resistant spider mite [Tetranychus urtícae solvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylarylpolyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with said amount of solvent and said amount of emulsifier, and the concentrate obtained is diluted with water q and the desired concentration.

The bean plants are sprayed with the active ingredient until dripping. (Phaseolus vulgaris). Treated plants are heavily infested with European spider mite (Tetranychus urticae.) At all developmental stages.

After a period of time below, mortality was found to be. expressed in. . %. 100% means that all spider mites have been killed, 0% means that none of the mites have been killed.

Active substances, active substance concentrations, evaluation time and results obtained are given in Table E below:

199506 25 Table Ε 18 Test for resistant spider mite (Tetranychus) active substance concentration of active substance in% mortality in% po 2 days

O

II (CH3O) p-CH-CCl3

OH.

(known)

With OCHF-CHa-Cl wz

CH 3 O - P \. NH2.

O OCHF-CH2-Cl

11

C2H5O-p

X

NH - C 3 H 7 -ISO

0.1

0.1

0.1

Example F

LT100 - test for two-winged insects: housefly (Musea domestica) solvent: acetone parts by weight of the active substance are dissolved in 1000 parts by volume of the solvent and the solution is diluted with another solvent to the desired concentration.

2.5 ml of the drug solution was pipetted into a Petri dish, at the bottom of which a circular filter paper having a diameter of about 9.5 centimeters was placed. Leave the petri dish exposed to stand until the solvent is completely evaporated. Depending on the concentration of the active substance solution, the amount of active substance, based on m ^{2 of} filter paper, is of varying amounts. About 25 specimens of test insects are then transferred to a Petri dish and the dish is covered with a glass lid.

The condition of the test insects is continuously monitored and the time to 100% mortality is determined.

Experimental 'insects, active substances,' active substance concentrations' times at which 100% mortality occurs are given in Table F below:

Table F

Active substance

LTioo - Two-winged Est (Musea domestlca)

LT100 concentration of active substance in hours in 'solution' (%)

O

II

CC10 — CH — P— (OCHO) 2

- I

Oh

0.002 6 = 0 (known)

F О ОСНз

II и /

C1-CH2-CH-O-P

X

NH2

0,00 / 6

1995OB

Active substance

Concentration of LT 10o of the active substance in hours in solution (%)

F O C2H5 · Hi ·

Cl — CHř — CH — O — P \

nh ₂

0,002

F O OC2H5

11

Cl — CH2 — CH — O — P \

N (C 2 H 5) 2

0,002

F О OC2H5

II 1 /

CI — CH2 — CC — O — P /

NH — CH

CH3 / CH3

0,002

The preparation of the active compounds according to the invention is illustrated by the following examples, which are not to be construed as limiting.

Example 1

35 g (0.4 mol) of morpholine are added to a solution of 22 g (0.1 mol) of phosphoric acid O- (1-fluoro-2-chloro-ethyl ester) in 250 ml of benzene at 20-25 ° C, the reaction mixture is stirred for 3 hours. The mother liquors were evaporated and the residue was recrystallized from ethyl acetate-ligroin to give 22 g (70% of theory) of O- (1-fluoro-2-chloroethyl) ester-dimorpholide, m.p. mp 90-92 ° C.

Example 2

C2H5O O \ 11 p — o — CHF — HH2 — Cl /

ISO-C3H7-NH

To a solution of 43.1 g of phosphoric acid O- (1-fluoro-2-chloroethyl) ester dichloride in 100 ml of diethyl ether was added dropwise with stirring and cooling at 20-30 ° C over a period of 2 hours 23.6 g of isopropylamine dissolved in 30 ml of ether. After 20 hours, the precipitated isopropylamine hydrochloride (20 grams) was filtered off with suction to a ethereal solution of the thus obtained O- (1-fluorocyclohexyl) -N-isoc propyl phosphamide chloride, dropwise with stirring and cooling, and a solution of 9.5 grams of ethanol was added dropwise. 22 g of triethylamine in 200 ml of diethyl ether are added, the reaction mixture is stirred at room temperature for 10 hours, then the precipitated triethylamine hydrochloride is filtered off with suction and the ether is distilled off under normal pressure. The reaction product was separated by distillation in a film evaporator at 150 [deg.] C. at a pressure of 40 Pa and separated from - high-boiling, by-products to give - 35 g (70% of theory) of O-ethyl-O- (1- (fluoro-2)). -chloroethyl) -N-1-isopropyl ester of phosphoric acid at a boiling point of 131 to 133 ° C / 67 Pa.

Example - 3

and)

Cl - S

Ml

P - O - HHF - CH 2 - Cl / CH 2 O

To a solution of thionophosphoric acid 47-g (0.2 mol) - (300 ml) toluene - 0.2 mol of sodium methoxide solution was added under cooling to the mixture. The mixture was stirred at 10 ° C for 1 min and washed twice with water. The organic phase is dried over sodium sulphate, the toluene is evaporated under reduced pressure and the residue is distilled. In a yield of 81%, thionophosphoric acid O-methyl-O- (1-fluoro-2-chloroethyl) diester chloride is obtained - b.p. 38-42 ° H / 0.5 mm Hg.

199508

(b)

CH5O S \ II

P — O — CHF — CH2 — Cl /

NHž

To a solution of 25 g (0.1 mol) of O-methyl-O- (1-fluoro-6-chloroethyl) di-thionophosphoric acid dihydrochloride in 200 ml of acetonitrile is added ammonia at ψ 20 ° C until the reaction is complete. The reaction mixture is poured into water, shaken with toluene, the organic phase is washed with water, dried over sodium sulphate, the toluene is evaporated and the residue is distilled under very reduced pressure. 16 g (77% of theory) of ion-methyl-O- (1-fluoro-2-chloroethyl) diesteramide thionophosphoric acid having a refractive index nD ²³ = 1.4950 were obtained.

Example 4

and)

Cl \ II

P — O — CHF — CH2 — Cl /

CH3O

55 grams of vinyl fluoride and 70 grams of chlorine are simultaneously introduced into 308 g of phosphoric acid O-dimethyldiesterchloride while cooling and stirring at a temperature of from -5 ° C to 0 ° C. After completion of the reaction, the mixture was first degassed under reduced pressure at room temperature and then subjected to fractional distillation. 143 g (69% of theory) of phosphoric acid O-methyl-O- (1-fluoro-2-chloroethyl) diester chloride are obtained, b.p. 69 DEG-72 DEG C./0.4 mbar.

(b)

To a solution of 11 g (0.05 mol) of O-methyl-O- [1-fluoro-2- (4-methyl-diester) -phosphoric acid diester chloride in 200 ml of benzene is added at 20-25 ° C at 20-25 ° C. 8.7 g (0.1 mol) of morpholine. The reaction mixture is stirred for a further 4 hours, then the precipitated morpholine hydrochloride is filtered off with suction, the solvent is evaporated off under vacuum and the residue is distilled under reduced pressure. 11 g (84% of theory) of O-methyl-O- (l-fluoro-2-phosphoric acid chlorethyljdiestermorfolidu · refractive index nD @ ²² = 1.4599.

Example 5 (C2 H5) 2N O

XI

P — O — CHF — CH2 — Cl /,

C2H5O

To a solution of 22.5 g of phosphoric acid O-ethyl-O- (1-fluoro-2-chloroethyl diester monochloride [prepared as in Example 4a) from phosphoric acid 0,0-diethyl diester chloride in 30 ml of diethyl ether was cooled with cooling and stirring, a solution of 15 g of diethylamine in 30 ml of ether is added dropwise at a temperature of 20 to 30 degrees Celsius. After 6 hours, the precipitated diethylamine hydrochloride is filtered off with suction, the precipitate is washed with ether, the ether is distilled off under normal pressure and the residue is purified by vacuum distillation. 25 g (95% of theory) of O-ethyl-O-1-fluoro-2-chloroethyl-N, N-diethyldiesteramide of phosphoric acid are obtained with a boiling point of 103-105 ° C / 67. Bye.

The following compounds can be obtained in an analogous manner to the previous examples:

Example ¢. product formula 6 C2H5O O \ ll P — O — CHF — CH2 — Cl δ (CH 3) 2 N 7 c, h op ₅ ² \ PO-CWF-CH5C1 €> ^z 8 ISSO-C3 H7 — NH O \ ll P — O — CHF — CH2 — C.l / sec.-CiHeO .). · 9 ISSO-C3 H7 — NH O \ ll P — O — CHF — CH2 —Cl / П-С4Н9О 10 ISO-C3H7 — NHO \ ll P — O — CHF — CH2 — Cl / П-СЗН70 ISO-C3H7 — NH O if \ i | P — O — CHF — CH2 — Cl / ISSO-C3H7O 12 From "" \ π ⁰ you \ p-0-CHF-CH 3 Cl 13 0 \\ θ PO ~ CHF CHrCl / _c2 * _W J 1 $ 14 C2H5 0 \ ll P — 0 — CHF — CH2 — Cl / Hafct 15 Dec (C ₂ H 5) 2 N 11 P-O-CHF-CH ₂ -Cl / CH ₂ H ₅ 16 0 II f (CH 3) 2 N 2 P - O - CHF - CH 2 - Cl 17 II (ISSO-C3H7-NH) ₂ P-O-CHF-CH2-Cl

Physical data Boiling point 92 ° C / 67 Pa Melting point 150 ° C n _D 29 = 1,4385 n _D 20 = 1,4395 n _D ²⁰ = 1,4428 n _D 20 = 1,4430 n _D 20 = 1,4550 Boiling point 125 to 30 ° C / 67 Pa Melting point 180 ° C Boiling point 100 ° C / 53 Pa Boiling point 84 to 87 ° C / 13 Pa n _D 24 = 1,4908

example no. product formula physical data (C2 H5) 2N O \ ll n _D 2 ° = 1.4345 18 СНзО — P — 0 — CHF — CH2 — CI 0 II 19 Dec C2H5-NH-P-O-CHF — СН2С1 \ ОСНз 0 II n _D 20 «1.4383 20 May C2H5 — NH — P — O — CHF — CH2Cl \ OCžHs 0 n _D 20 = 1.4400 ·· 21 C2H5-O-P-O-CHF-CHaCl n _D ²⁰ = 1.4425 \ HNCíHsn 0 II n _D ²⁰ = 1.4358 22nd C 2 H 5 -O-P-O-CHF-CH 2 Cl \ NH — СНз 0 II C2H5 — O — P — O — CHF — CHaCl 23 n _D ²⁰ = 1.4371 24 \ NH - CH - C2 H5 1 СНз C2H5O 0 \ ll n _D ²⁰ = 1.4385 P — O — CHF — CH2 — Cl z nC3H7NH СНзО 0 \ ll 25 P — 0 — CHF — СН2ВГ z n _D ²⁰ = 1.4551 (C2H5) 2 N 1 26 C2H5O 0 \ ll boiling point 125 ° C / 13 Pa P — 0 — CHD — СН2ВГ z C2H5NH C2H5O 0 \ ll P — O — CHF — CH2 Br n _D = 1.4550 ² 9

/

С2Н5 — CH — N

I н

СНз

example. C. product formula physical data 28 СНзО O XII · ' ^ ^ O-CH3F-O ^ 2Br / C2H5-N H n _D ² = 1.4541 AND 29 CH3O O X1 P — O — CHF — CHaBr / ' C2H5-CH-N I h , СНз  \ 9 30 СНзО О XII. · P — O — CHF — CH2Br / C2H5-N CH3, 31 C2H5O О XII P — O — CHF — CH2 Br /. C2H5-N. CH3 32 CH3O O XI . P — O — CHF — CH2Cl / C2H5-N. -Λ. CH3 - 33 C2H5O o XiII P — O — CHF — CH2Cl · / C2H5-N - AND CH5. 34 11-C3H7O · O X1II P — O — CHF — CH2Cl2 / C2H5-N 1 'CH3. 35 ^: 11-C 5 H 7 O O XII P —— O — CHF — CH2B1 ’. / C2H5-N.

CHs

9'506

Example no. product formula physical data 36 П-С3Н7О 0 \ ll P — O — CHF — CHBr / C2H5-CH-N W h СНз 37 W1-C5 O10 \ ll P — 0 — CHF — CH2Cl / C2H5-CH-N 1 η CHs 1 38 1-C 3 H 7 O 0 \ ll P — O — CHF — CHaBr / C2H5-CH-N 1 h CH3 t CH3 39 I-C 3 H 7 O 0 P — O — CHF — CH2Cl / C2 H5 — CH — N 1 h CH3 40 CH30 0 \ ll .. P — Q — CHF — CH2Cl / CICH2 — CH2 — NH 41 CH3O 0 • \ ll 4 P — 0 — CHF — CH2Br / CICH 2 —CH 2 —NH 42 C2H5O 0 \ ll P — 0 — CHF — CH2Cl / CICH 2 —CH 2 —NH 1 < 43 C2H5O 0 \ ll P-O — CHF-CH3'Br / CICH 2 —CH 2 —NH 44 CH3O 0 \ ll P — 0 — CHF — CH2Cl / C1CH2-CH-NH

СНз Example No Product Data Physical Data

СНзО O \ ll

P — O — CHF — СНгВг

OF

C1CH2 — CH — N

I ^H СНз

C2H5O

P — O — CHF — СНгВг

OF

CICH 2 —CH — N

I h

СНз

C2H5O o

XI

P-O-CHF — CH2Cl

OF

CICH 2 —CH — N

I h

СНз

C2H5O XII

P — O — CHF — CH2Cl

Z v

NCCH 2 —CH 2 —N ⁴

СНз

CIC2H4O O

XII

P — O — CHF — CH2Cl

OF

СНз — N

H

CICH 2 —CH 2 O O

XII

P-O-CHF — СНгВг

OF

CH3HN

CICH 2 —CH 2 O

XII

P — O — CHF — CH2Cl

OF

C2H5-HN

CICH 2 —CH 2 O O

XII

P — O — CHF — СНгВг /

C2H5-HN

CICH2 — CH2 — o

XII

P — O — CHF — СН2С1 Z (C2H5) 2N

example no. product formula physical data 54 CICHz — CHž — 0 0 XII P — 0 — CHF — СН2ВГ / (C2H5) 2 N 55 C 1 CH 2 —CH 2 --O 0 XII P — O — CHF — CH2Cl OF C2H5-CH-N 1 H СНз 56 C1CH2 — СНЮ 0 XII P — 0 — CHF — СНгВг OF C2H5-CH-N 1 h СНз and ! 57 C 1 CH 2 —CH 2 O XII P-0-CHF-СН2С1 Z C1-C3H7-N H 58 CICH 2 -CH 2 O 0 XII P — 0 — CHF — СН2ВГ z C1-C3H7-N H 59 C 1 CH 2 —CH 2 O XII P — 0 — CHF — СНгВг OF C2H5-N 1 СНз

W99506

Claims (2)

1. Insecticidal, acaricidal. and a nematicidal composition, characterized in that it contains O- (1-fluoro-2-halo-ethyl) -esteramide (thiono) phosphoric acid of the formula I as active ingredient Rl / M p— / R2 O — CHF — CH2 — Hal (I), Hal ¹ X, \ ill, P — O — CHF — CH2 — Hal (II), / R3 where Hal and X are as defined above, Hal ¹ represents a halogen atom, preferably chlorine and R ³ represents the radical R ² or Hal ¹ as defined above, reacted with an amine of the formula (III) where R ³ is R @ 1 and R @ 1 are each independently hydrogen or a straight or branched (C1 -C4) alkyl group, or both together with the nitrogen atom to which they are attached form a morpholine or piperidine ring, R2 is a straight or branched (C1-C4) alkoxy or alkyl (C1-C2) alkyl radical, Hal chlorine or bromine and X oxygen or. sulfur. 2. Process according to claim 1, characterized in that the compounds of the formula II are used R /. HN. (III). \ r1. where R 2 and R 1 are as defined above, optionally in the presence of an acid acceptor and optionally in the presence of a solvent, at a temperature of 0 to 100 ° C, preferably 20 to 40 ° C, provided that for the preparation of compounds of formula I R2 'is an alkoxy group as defined above, X is O and R, R1 and Hal are as defined above, the reaction product of a compound of formula (II) wherein R3' is. the remainder of Hal1, oxygen atom X and Hal and Hal are as defined above; with an amine of formula III, is reacted with an alkanol corresponding to the radical R @ 2, optionally in the form of an alkali metal or alkaline earth metal salt, or in the presence of an acid acceptor, and optionally in the presence of a solvent.