CA1069893A - O-alkyl-o-(7-alkyl-pyrazolo-(1,5-a) pyrimidin-(2)yl) -(thiono)-phosphoric (phosphonic) acid esters and ester-amides - Google Patents

Abstract

0-ALKYL-0-[7-ALKYL-PYRAZOLO-(1,5-a)PYRIMIDIN-(2)YL]-(THIONO)-PHOSPHORIC(PHOSPHONIC) ACID
ESTERS AND ESTER-AMIDES
Abstract 0-Alkyl-0-[7-alkyl-pyrazolo (1,5-a)pyrimidin(2)yl]-(thiono)-phosphoric(phosphonic) acid esters and ester-amides of the formula

Description

The pr~ent inventlon rel~te~ to nnd ha~ for itB
objecta the provision of pflrticul~r new ~ubstltuted 0-slkyl-0-[7-~lkyl-pyr~zolo (1 ,5-D )pyrimldin (2)yl] - ('chiono) ~phosphorlc-(pho~phonic) acid esters ~nd ester-~mides which pos3es~
:0 ~rthropodicid~l ~nd nem~ticid~l propertie~, ~ctlv~ compositlons - . !
ln the form of mixtures of such compound8 wi'ch ~olid ~nd liquid dispersible c~rrier vehicles, ~nd methods for producing ~uch compound8 and for u~lng 8uch compound~ in ~ I
new w~y especi~lly for comb~ting pest~, e.g. ~rthropod~ ~nd Le ~ 16 734 1 ~

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nematodes, with other an~ further objects becoming ~pparent from a ~tudy of the wlthin 8peci1c~tion ~nd acoomp~nying example~.
It is known rom Belgl~n P~tent Speciflc~tion 769,702 that 0-pyrazolopyrimidine(th~ono)-phosphoric(phosphonlc) acid e~ters, such as, for ex~mple, 0,0-dimethyl- (Compound A) ~nd 0,0-diethyl-0-[7-methylpyr~zolo(1,5-a~-pyrim~din~2)yl]~
(Compound B) or 0,0 dimethyl- (Compound C) ~nd 0,0-diethyl-0-~3-chloro-7-methyl-pyrazolo(1,5-~)pyrimidin(2)yl]-thiono-phosphoric ~cid ester (Compound D) and 0-sec.-butyl-0-[3-bromo-7-methyl-pyrazolo(1,5-a~pyrimidin(2)yl]~thlonometh~nephoRphonic ~cid e8ter (Compound E), exhibit a pesticld~l~ especially an insectlcidal ~nd ac~rlcid~ ction.
The present invention provides, ~8 new compound8 7 the O-pyrazolopyrimidine (thiono)-phosphoric (phosphonic) ~cid e~ters ~nd ester-amides of the general forr~la ~2 in which Rl is ~lkoxy with 1 to 6 c~rbon ~tom8, i8 ~lkyl or ~Lkoxy e~ch with 1 to 4 c~rbon ~toms, or alkyl~mino with up to 6 c~rbon atoms, R3 i8 hydrogen or h~logen, R~ i8 ~lkyl with 2 to 6 c~rbon ~tom~J ~nd X is oxygen or 8ulfur, Le A 16 734

-2-. . , . .

;9~3~3 Preferably, R1 repre~ent~ ~trai~ht~chain or br~nchea alkoxy with 1 to 4 carbon atoms, R2 repre~ents straight-chain or branched alkoxy or alkyl ea h with 1 to 3 carbon atoms, or monoalkylem:Lno with 1 to 4 carbon atoms, R3 represents hydrogen, chlorine or bromine, R4 represents straight-chain or branched alkyl with 2 to 4 carbon atoms and X represents sul~ur.
Surprisingly, the 0-pyrazolopyrimidine(thiono)-phosphoric(phosphonic) acid esters and ester-amides according to the invention exhibit a substantially greater insecticidal, .:
acaricidal and nematicidal action than th0 previously known compounds of analogous structure and of the same type of acti.on. The compounds according to the invention thus represent a genuine enrichment of the art.
The present invention also provides a process ~or the preparation of an 0-pyrazolopyrimidine(thiono) phosphoric (phoæphonic) acid ester or ester-amide of the formula (I), in which a (thiono)phosphoric(phosphonic) acid ester halide or ester-amide halide, of the general formula 2 P-Hal (II) in which Rl, R2 and X have the above-mentioned meanings and Hal represents halogen, preferably chlorine or bromine, is reacted, if eppropriate in the presence of a diluent or solvent, with a 2 hydroxypyrazolopyrimidine derivative of the --general formNla N0 ~ ~ (III), ~4 in which R3 ~nd R4 have the above-mentioned meanings, the latter being employed as such, in the presence o~ an acid acceptor, or in the ~orm of an alkali metal salt, alkaline earth metal salt or a~monium salt.
If 0,0-diethyl-phosphoric acid ester chloride and 2-hydroxy-7-ethyl-pyrazolo(1,5-a)-pyrimidine are used as starting materials, the course of the reaction can be rep-resented by the following equation:

C2H5~p Cl + ~ )~1~ ~, (IIa) (IIIa) acid 0 acceptor C2H5 \ 11 0~ , -HCl 2 5 (4) 2 5 The (thiono)phosphoric(phosphonic) acid ester halides and ester-amide halides (II) to be used as starting materials are known and can be prepared in accordance with generally customary processes. The follo~ing may be mentioned as individual examples of these compounds: 0,0-dimethyl-, 0,0-diethyl-, 0,O~di-n~propyl-, 0,0-di-isopropyl-~ 0-ethyl- ~;
0-n-butyl-, 0-ethyl-0-isobutyl-, 0-ethyl-0-sec.-butyl~
0-ethyl-0-tert.-butyl-, 0-n-propyl-0-sec.-butyl- and 0-ethyl-0-n-propyl-phosphoric acid diester chloride or bromide and the . , ~
corresponding thiono analogues, 0-methyl-, 0-ethyl-, 0-n-propyl-, 0-isopropyl-, 0-n-butyl-, 0 isobwtyl-, 0 sec.-butyl-and 0-tert.-butyl-methane-, -ethane-, -n-propane- and -isopropane-phosphonic acid ester chloride or bromide and the corresponding thiono analoguea, and 0-methyl-N-methyl-, _ 1~ _ ~ o6~8~3 0-ethyl~N-ethyl-, 0-n-propyl-N-n-propyl-, 0-i~opropyl-N-I
isopropyl-, 0-n-butyl-N-n-butyl-, 0-ethyl-N-n-propyl-, OL
ethyl-N-isopropyl-, 0-ethyl-N-n-butyl-, 0-ethyl-N-isobut~
0-ethyl-N-~ec.-butyl-, 0-n-propyl-N-ethyl-, 0-n-propyl-N-n-butyl-, 0-n-propyl-N-i~obutyl-, 0-n propyl-N-~ec,-butyl-, 0-i~opropyl-N-ethyl-, O~i~opropyl-N-n~butyl-, 0-i~opropyl~-i~obutyl- and 0-isopropyl-N~sec.-butyl-phosphoric acid ester-amide chloride or bromide and the corre~ponding thiono analogues.
The 2-hydroxy-pyrazolo(1,5-a)pyrimidine derivati~e~
(III) to be u~ed a~ ~tarting mater~ are new. They can be prepared, ~or example, by reactir~ 3-aminopyrazolone-(5), in ethanol saturated with hydrogen chloride ga~, with 1-chlorovinyl-(2) alkyl ketones, thu~:

0 ~ + ~4-C-CH~CHCl > H

in which R4 ha~ the above-mentioned meaning~
~he product~ halogenated in the 3-po~ition are obtained there~rom i~ cu~tomary ma~ner by halogenation.
~he ~ollowing may be me~tioned a~ individual ~ample~:

3-chloro-7-ethyl-, 3-chloro-7-~-propyl-~ ~-chloro-7-iso-propyl-, 3-chloro-7-n-butyl-, 3~chloro-7-i~obutyl-, 3-chloro-7-~ec.-butyl-, 3-chloro-7-tert.-butyl-, 3-bromo-7-ethyl-, 3-bromo-7-n-propyl-, 3-bromo-7-i~opropyl-, 3-bromo-7-n-butyl-, 3-bromo-7-i~obutyl-, 3-bromo-7-~eo.-butyl- a~d 3-bromo-7-tert.-butyl-2-hydro~gpyrazolo(1,5-a)pyrimidlne, ~e A 16 7~4 _ 5 _ 8~;~

The proce~ of preparation is preferably carried out in the presence of a suitable ~olvent or diluent Practically all inert organic ~olvent~ can be used for thi9 purpo~e, especially allphatic and aromatlc, optionally chlorinated~
hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dloxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone;
nitriles, for example acetonitrile and propionitrile; and formamides, especially dimethylforma~ide.
All customary acid-binding agents can be used as acid ~ ~
acceptors. Alkali metal carbonates and alkali metal alcoho-lates, such as sodium carbonate or potassium carbonate, sodium methylate and ethylate or potassium methylate and ethylate, have proved particularly suitable, as have aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethyl-amine, dimethylaniline, dimethylbenzylamine and pyridine.
The reaction temperature can be varied within a fairly wide range. In general, temperatures between 0 and 100 C, preferably from 15 to 35C, are used.
The reaction is in general carried out under normal pressure.
To carry out the process, the startine materials are in most cases employed in equimolar amounts. An excess of one or the other reactant produces no significant advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents and in the presence of an acid acceptor, at the stated temperatures, after stirring ~or ~ 9893 from one to ~everal hours at the stated temperatures, t~e reaction mixture is worked up by adding ice water to it.
Either the product thereupon directly precipita~es in a solid form, in wbich case it is filtered of~, washed and, ~
appropriate, recrystal]ized, or the mixture is extracted with an organic solvent, preferably methylene chloride. After washing and dryin~ the extract, the solvent is removed under reduced pressure.
The compounds according to the invention are in most caæes obtained in a crystalline form and are characterized by their melting point. However, if they are obtained in the form o~ oils, which are mostly yellowish-red, and which cannot be distilled without decompositionD these oils are freed from the last volatile constituents by æo-called "slight distillation", that is to say prolonged heating under reduced pressure to moderately ele~ated temperatures, and are purified in this way. In that case, they are characterized by the refractive index.
As already mentioned, the new 0-pyrazolopyrimidine-(thiono)-phosphoric~phosphonic) acid esters and ester-amides are distinguished by an excellent insecticidal, acaricidal and nematicidal activity. They are active against plant pests, pests harmful to health and pests of stored products. In this respect, they have a good action against both sucking and biting insects and against mites (Acarina).
For these reasons, the products according to the invention may be employed successfully as pesticides in plant protection and the protection o~ stored products, as well as in the hygiene fleld.
~he active compound~ are well tolerated by plants, ha~e ;

3~3~3 a favorable level o~ toxicity to warm-blooded animals, ~nd can be used for combQtlne arthropod pests, especlally lnsects, arachnids and nematodes which are encountered ln agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensltive and resistant specles and against all or some stages of development.
The above~mentioned pests include: from the class of the Isopoda, for example Oniscus asellus, Armadillidium ~
and Porcelllo scaber; from the class of the Diplopoda, for example Blaniulus ~uttulatus; from the class of the Chilopoda, for example Geophilus carpophagus and Scutigera spec.; from the class of the Symphyla, for example Scutigerella immaculata;
from the class of the Thysanura, for example, Lepisma saccharina; from the class of the Collembola, for example 5ay~gE~ armatus; from the class of the Orthoptera, for : .
example Blatta orientalis, PeriPlaneta americana, Leucophaea ;
maderae, Blatella germanica, Acheta domesticus, Gryllotslpa :-:
spp., Locusta migratoria mi~ratorloides, Melanoplus different- ~ -ialis and Schistocerca eregaria; from the class of the Dermaptera, for example ~orficula auricularia; from the class of the Isoptera, for example Reticulitermes spp.; from the class of the Anoplura, for example Phylloxera vastatrix, Pem~higus spp., Pediculus humanus corporis, _aemato~inus spp.
and Linogr.athus spp.; from the class of the Mallophaga, for example Trlchodectes spp. and Damalinea app.; from the class of the Thysanoptera, for example Hercinothrips femoralis and Thrips tsbaci, ~rom the class of the Heteroptera, for example Eur~ast0r spp., Dysdercu~ intermedius, Piesma auadrata, Cimex _ctularius, Rhodniua ~rolixus and Triatoma ; : .

g;~

~pp.; ~rom the cla~s Or the Homop-tera, for example Alet~odes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aph-ls gossypii~ Brevicor~ brassicae, Crvptomyzus ribis, Doralis ~abae, Doralis pomi, Eriosoma lanigerum, ~ E~E~ arundinis~
avenae, Myzus 9pp., Phorodon humuli, Rhopalosiphum __ padi, Em~oasca spp., Euscelis bilobatus, Nephotettix cincticePs, Lecanium corni, Saissetia oleae, aodel hax striatellus, Nilaparvata lu~ens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Ps~lla spp.; from the class o~ the Lepidoptera, for example PectinoPhora ~oss~piella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta ~ Plutella maculipennis, Malocosoma neUstria, Euproctis 5~3~EE~ h~3@E~E~ spp., Bucculatrix thurberiella, Phyllocnistis citrella, A~rGtis spp., Euxoa spp., Feltia spp., Earias insulana, He]iothis spp., Laphygma Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, CarPocaPsa pomonella, Pieri~ spp., Chilo spp., Pyrausta nubil~lis, EPhestia kuhniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona maenanima and Tortrix viridana; from the class of the Coleoptera, for e~ample, Anobium punctatum, ~æsP~E~E~
dominica, Bruchidius obtectus, hcanthoscelides obtectus, H~lotrupes ~ Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes ~ysocephala, , Epilachna varivestis, Atomaria Bpp., Oryzaephilus !urina~ensis, Anthonomus spp., Sitophilus spp., Otiorrh~nchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilus, Hypera Postica, DermQstes spp., Tro~oderma spp., Anthrenus ~pp., Attagenus Bpp., L~ctu~ spp., Meli~ethes aeneu~, Ptinus Bpp., _ g _ 98~3~

Niptus hololeuous, ~b~ Tribollurn spp., 'renebrio molitor, Agrlotes ~pp., Conoderus ~pp., Melolontha melolontha, Amphimallon solstitialls and Costelytra zealandica; from the class of the H~menoptera, ~or example Diprion spp., Hoplocame~ ;
spp., Monomorium pharaonis and Vesta spp.; from the clas~ of the Diptera, ~or example Aedes ~pp., Anophele~ ~pp., Culex spp., Drosophila melanogaster, Musca spp., Fannia ~PP-, 5~ eb~E~
__ erythrocephala Lucilia spp., ~ spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox~s spp., Oestrus spp., H~poderma spp., Tabanus 9pp., Tannia spp., Bibio hortulanus, :~:
Oscinella frit, Phorbia spp., ~ y~ Hyo~cyami, Ceratitis capitata~ Dacus oleae and Tipula ~ludosa; from the class of the SiphonaPtera~ for example XenoPsylla cheoPis and Ceratphyllus spp., from the class of the Arachnida, for example Scorpio mauru~ and Latrodectus mactans, from the ~.
class of the Acarina, for example, Acarus siro, Ar~as spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Ph!yllocoptruta oleivora, ~ a~ spp., Rhipicelphalus spp., Amblyomma spp., Hyalomma ~pp., Ixodes spp., Psoroptes spp., Chorioptes ~PP-, ~E~YE~ spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., and Tetranychus spp.
The plant-parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semiPenetrans, Heterodera spp., ~ Ya~ spp, Aphelen-choides spp., Longidorus spp., Xi~hinema spp. and Trichodorus spp.

~o~9~

When u~ed again~t hygiene pest~ and pe~t3 o~ stored products, the activc compounds are distinguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.
The active co~pounds according to the inskant invention can be utilized, if desired, in the form of the usual formulations or coD~ositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders o-f the type usable in conventional pesti-cide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concen-trates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compo~itions, for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist ~ormulations.
These are prepared in kno~m manner, for instance by extending the active compound~ with conventional pesticide disper~ible liquid diluent carriers and/or dispersible 601id carriers optionally with the use of carrier vehicle assistant~, e.g. conventional pesticide surface-active agent~, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where ~ ' ' ' ' '- ~, .

~ 3t393 water is used as dilucnt, organ-Lc solvents rna~J be added as a~iliary solvents. The ~ollowing may b~ chie~ly considered ~or use as conventional carrier vehlcles ~or this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g.
benzene, toluene, xylene, alkyl naphthalenes, etc.), ~ -halogenated, especially chorinated, aromatic hydrocar~ons (e.g. chlorobenzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleu~ or mineral oil ~ractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g.
ethanolan~ne, etc.)~ amides (e.g. dimethyl formamide~ etc.), sulfoxides (e.g. dimethyl sulfo~ide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ?
ketone, cyclohexanone, etc.), and/or water; as solid carriers, ~round natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmor-illonite or diatomaceouæ earth, and ground synthetic minerals, such as hi~hly-dispersed silicic acid, alumina and silicates; as solid carriers ~or granules; crushed ;
and fractionated natural rocks 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; whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. ~ur~ace-active agentfl, for this purpose: emulsifying aeents, such afl non-ionic and/or .

', : -"` ' ' ' 98~3 anion:Lc emulsifyine aeent~ .g. polyethyl0ne oxide e~tert o~ fatty acids, polyethylene oxide ethers of fatty alcohol~, alkyl sulf~tes, alkyl ~ul~onates, aryl sul~onates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magneæium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and 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 dyestuffs and metal phthalocyanine dyestuffs, and traca nutrients such as salt~ of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Such acti~e compounds may be employed alone or in the form of mixtures with one another and/or with such ~olid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other arthropodicides and nematicides, or fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

. .
,' ' ~ ' ' ' ,: .

1~6913~3 A~ concerns commercially marketed prep~ration~, these generally contemplate carrier co~position mixtures in which the active compound ia present in an amount substantiall1J
between about 0.1-95~ by weight~ and preferably 0.5-90% by weight, of the mixture, whereas carrier co~position mixtures suitable for direct application or field application generally contemplate thosé in which the active compound is present in an amol~t substantially between about 0.0000001-100, preferably 0.01-10~, by weight of the mixture. Thus, the present invention contemplates overall compositiong which comprise mixtures of a conventional dispersible carrier such as (1) a dispersible inert finely divided carrier solid, and/or ~2) a dispersible carrier liquid such as an inert organic solvent and/or water, pre~erably including a surface-active effective amount of a carrier vehicle - ~ ?
assistant, e.g. a surface~active agent, such as an emulsifyine -agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.01-95%, by weight of the mixture.
The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition côntaining the same, via very effective atomizing equipment, in finely divided form, é.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hect~re are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g¦hectare, are sufficient. In this process it is possible to use highly concentrated liquid compos-: ' ~ - : -.: ' . ' ' .
: , 1 ~ 6 ~ ~ 9 3 ition~ with s~id liquid c~rrier vehiclea cont~lnlng from ~bout 20 to about 95% by weight of the ~ctive compound or even the 10~/o ~ctive ~ubst~nce ~lone, e.g. ~bo~t 20-10~/o by weight of the ~ctive compound.
Furthermore, the presen~ invention contempl~e~
method~ of selec~ively killing, comba~ing or controlling pe~ts, e.g. ~rthropods ~nd nem~todes, which comprisea ~pplying to ~ le~st one of correspondlngly (a) ~uch ~rthropods, (b) such nem~todes, ~nd (c) ~he corre~ponding habit~t thereofJ
i,e. the locu~ to be protec~ed, e,g. to ~ growing crop, to ~n ares where ~ crop i8 to be grown or to ~ domestic flnim~l, fl correspondingly combative or toxic ~mount, i.e. ~n arthropod-icidally or nema~icid~lly effec~ve flmount, of the particul~r acti~e compound of the invention ~lons or together with ~
carrier vehicle ~ noted ~bove. The inst~nt formulations or compositions are ~pplied in the usu~l manner, for in~t~nce by spr~ying, ~tomiz$ng, vapori~ing, scattering, dusting, waterin~, squir~ing, sprinkling, pourln~, fumigating, ~nd the like.
It will be re~lized, of course1 th~t the concen-l:r~tion of ~he pQrticul~r ~ctive compound utilized in ~dmixture with the c~rrier vehicle will depend upon the intended appllc~tion. Therefore, in speci~l ca8es it 18 possible to go ~bove or below the ~forementioned con en-tr~tion range~.

Le A 16 734 3~3 ~he unexpected superiority arld outstanding activit~
of the particular new compo~lds o~ the pres0nt lnvention are illustrated, without limitation, by the foll~ring examples:
EY.ample 1 -Phaedon la~vae 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 weiBht of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with ~rater to the desired concentration. ~:
Cabbage leaves (Brassica oleracea) were sprayed ~ith the preparation of the active compound until dripping wet and were then infested with mustard beetle larvae (Phaedon cochlerri~e).
After the specified periods of time, the degree of de~truction was determined in %: 100% means that all of the beetle larvae had been killed whereas 0% means that none of the beetle larYae had been killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen -~
from the following table: :~ :
, "

:

389~3 Table 1 (Phaedon larvae test) Active compound Active com- Degree o~
pound con- destruction centration in % after ~-g (CH30)2P-0 ~ o.olol 100 ~ N ~ r (known ) (A~

(CH30)2P-0 ~ Cl 0 001 100 ~ N
(known) ~

~C2~0)2~-0~;;;3~ 0 01 lOo ; (known) (CP30)2P-0 ~ Cl O.Ol lO0 ~ 0.001 100 (18) C2 5 (CH30)2P-0 Cl ~ O . 01 100 N~N~ O . 001 100 (13) C3H7-iso _b 1 e 1 (contirlued) aedon larvae test ) Active compound Active com- Degree oY
pound con- de~truction centration in ~ after in % ~ da~r~
S
(C2H50) 2P-O--j r Cl 0.01 100 `N~ 0.001 100 S

Il Cl (C2H5) 2P-~ 0 001 10oo ~N~N
(2) C3H7 n S

(C2H5o) 2P-~cl 0 001 1000 M~ ~N
(6) ~J
C3H7-iso s ll Cl ( C 2H 50 ) 2P-C 4H~i so C2H5~ 1I Cl ~P-O~/ 0.O.l 100 2 5 ~M -l 100 (11) /~

~e A 16 7~4 -18-'~0 ~9 8 9 3 T a b l e 1 (continued) ~Phaedon larvae te~t) Active compound Active com- Degree o~
pound con- de~truction centration in ~0 after in ~/o~ davs C2H5~ 11 n-C3H70/ ~3~N 0.01100 ,W 0. 001 100 C2~5 C2H5~ 11 o~ 0,01 100 n C3 7 N~NlN 0. 001 100 /~
(14) C2H5 Example 2 test (oontact action) Solvent: 3 parts by weight o~ acetone Emulsi~ier: 1 part by weight o~ alkylaryl polyglycol ether To produce a ~uitable preparation o~ active compound, 1 part by weight o~ the active compound wa~ mi~ed with the ~tated amount o~ ~olvent containing the ~tated amou~t o~
emulsi~ier and the concentrate wa~ diluted with water to the de~ired concentration.
Cabbage plant~ (Bra~ica ga~ ) which had been heavily infe~ted with peach aphid~ 3~ er~icae) were .~prayed with the preparation o~ the active compound until drippin~ wet.
A~ter the ~peci~ied period~ o~ time, the degree o~
de~truction wa~ determined a~ a per¢entage: lO0~ mean~ that all the aphid~ were killed wherea~ 0% mean~ that none o~ the aphide were killed.

~e A 16 7~4 -19-~9~3~3 ~ he active compoundq~ the concentrations o~ the active compounds~ bhe evaluation times and the re~ult~ can be ~een from the following table:

(M~zus test) Active compound Active com- Degree o~
pound con- destruction centration in % after in l day I~ C1 (CH30) 2P-0~ 0001 99 ~1 1 0, 001 4 (known) w~N~ \N .l (C) ~,~ ' 11 '.
(CH30) 2P-0~ 0.01 100 ~w ~W 0.001 97 ~ ~ 0.0001 35 (9) C H

ll Cl (CH30) 2P 0 ~ 0.01 100 ~ 00001 100 /~ O. 0001 55 (13) C H7-~So '; ' S '' Il (C2H50)2p-o ll 1 0.01 100 ~ 0 001 100 ~e A 16 734 -20-.

9 ~

a b 1 e 2 (continued) ~ te~t) Active compound Active com- Degree o~
pound con- de3truction centration in % a~ter _ _ in_Yo 1 da.Y
ll Cl (C2~5) 2P 0 ll ~ 0.01 100 N~N N 0.001 95 ~ 0, 0001 5 (2)oC3H7 n ~P 0 ~ 0. 01 l 00 C2H5 J~ 0.001 100 ~N N 0. 0001 75 ( 1 1 ) C 2H 5 C2H50~ 11 n~C3H7~ 7~ 0. 01 100 N~N N 0 . 001 1 00 (15) ~ ' Doralis test (3~temic action) Solvent: 3 part~ by weight of ace~one Emul~i~ier: 1 part by weight oP alkylaryl polyglycol ether To produce a suitable preparation Or active compound, 1 part by wei~ht o~ active compound wa~ mixed with the ~tated amount Or ~ol~ent ~nd the ~tated amount of emulsi~ier, and the conc~ntrate ~a~ diluted with water to the de~ired conoentration.

~e A 16 734 -21-lO~9B93 Bean plants (Vicia ~aba) which had been he~vily in~e~ted with the bean aphid (Doralis fabae) were watered with the preparation of the active compound ~o that this preparation penetrated into the soil without wettin~ the leave~ o~ the bean plants. ~he active compound wa~ taken up ~rom the 30il by the bean plants and thus pa3sed to the in~ested lea~es.
After the specified periods of time, the degree of destruction waq determined a~ a percentage. 100% means that all the aphids were killed; O~o means that none o~ the aphids were killed.
~he acti~e compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the ~ollowing table:
T a b l e 3 .
(Dorali~ te3t/systemic ac~ion) Active compound Acti~e com- Deeree of pound con- destruction centration in % a~ter _ _ ~ in ~o 4 daYs ll C1 (C2HsO)2p -r-- ~ 0-1 N~N N
(~own) 1\ J
(D) /~"

S
ll/O-C4H9-~ec 3 o sr ~ O. 1 0 N`N ~N

(E) CH3 ~e A 16 734 -22-1~69~393 T a b 1 e 3 ~continued) (Dorali~ te~t/~yYtemic action) Active compound Active com- Degree of pound con- de~truction centration in ~o a~ter ln ~ 4 day~ _ S

(CH) 2P- ll 3~ 0.1 100 (9~ C2H5 (C2H50)2P-0 ~ 0.1 100 ~`

(4) c2H5 1~
(C2H50)2P ~ 3 ~
N`N N
,W

(17) O

C2H$0)2P ~ 0.1 100 `N~N
,W
(16) C2H5 Example 4 ~E~13~Y~ te8t (re~i3tant) .Solvent: 3 part~ by weight o~ acetone Emulsi~ler: 1 part by weieht o~ alkylaryl polygly¢ol ether ~o produce a ~uitable preparation o~ active compound, 1 part by weight o~ the active compound wa~ mixed with the ~e A 16 7~4 . . - , . :- . , ~ ~ . "

~:)691393 ~tated amount of solvent and the stated amount o~ emulsi~ier and the concentrate was diluted with water to the desired concentration.
Bean plants (Phaseolus vul~aris) which were heavily infested with the two-spotted spider mite (Tetra~Ychus urticae) in all stages of development were sprayed with the preparation of the active compound until dripping wet.
After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the spider mite~ were killed whereas OYo means that none o~ the spider mites were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be 3een from the following table:
T a b 1 e 4 (Tetra Ychus test) Active compounds Active com- Degree o~
pound con- destruction centration in ~ a~ter Il /0-C4Hg-sec.
~0~r O. 1 0 (known) ~` N N
~) ,~

. S
3 ~ ~ o.l 99 (9) C2~5 Le A 16 7~4 -24-8~3~

T a b l e 4 (continued) ~ 3a~b9~ test) Active compound Active c~- Degree of pound con- de~truction centration in ~ after _ in % 2 da.v~
S

tCH30)2P-O~T~ ~
N~N N

S
Il Cl (C~30)2P-0 ~ 0.1 9 (13) c ~-iso S
(C2H50)2P 0 r ll 0.1 98 ~ - N

(4) C2H5 o - (C2H50 ) 2P-O ~
N`N N 0-1 80 (17) C2H5 Il Cl ~C2H50) 2P-O I 1/

N~N ~ 0.1 98 (1 ) /~

Il Cl ( 2 5 )2P ~l ~ 0.1 98 (16) C/ W

~e A 16 734 -25-10~8~3 T a b l e 4 (continued) (Tetran~Y-c--hus te~t) Active compound Active com- Degree o~
pound con- de~truction centration in % a~ter in ~ 2 da.Yg (C2H50)2P-0~

N`M' 0.1 80 /~ .
(6) S C3H -iso 2 5 ~ p_0 Cl C2H5'' N~N 001 99 :~ C H
(1 l ) 2 5 S

\P-O 1 n-C3~7' N~N 0.1 99 /~
t15) c2~5 s ..
C2H5 ll Cl ~p-o--n-C3H70 li I
N~N N 0.1 90 /~
~` ' (1~) C2H5 ~e A 16 734 -26-... .

~ ~ ~ 9 8 9 3 i~'xample 5 Tc~t insect: Phorbia antiqu~ g~UbB in the ~oil Solvent: 3 parts by weight o~ acetone 'j l~mulsi~ier: l part by weight of alkylaryl polyglycol ether To produce a suitable preparation oP active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate wa~ diluted with water to the de~ired concentration.
The preparation of active compound was intimately mixed with the 50il. The concentration o~ the active compound in the preparation was practically immaterial, the only decisive factor bein~ the amount by weight of active compound per unit ~olume of soil, which is quoted hereinafter in ppm (= mg/l). The soil was filled into pots ~nd the pots were left to stand at room temperature.
After 24 hours the te~t insects were introduced into the treated soil and after a further 2 to 7 days the degree of effectivenesq of the active compound was determined in % by counting the dead and live test insects. The degree of effectivenese was 100~o if all the test in~ects had been killed and was O~o i~ exactly as many test insects were still alive as in the case of the untreated control.
The active compounds, amounts u~ed and results can be seen from the table which follows:

~e A 16 7~4 -27-~0698~3 T a b 1 e 5 (Phorbia antiqua grubs in the qoil) ctive compound Degree o~ destruction in %
at an active compound con-S

C2HS ~ 11 P--O ~ _.
C 2 H 50 N~ ~ ~ N
( known ) )~
(B) c~l3 S

Il ~C4H9~Sec' CH3 P\
o ~ r O

( kncwn ) (~) ~

S ~, (C2H50)~-0 - ~Cl 1 00 N~ N

(1 ) C2H5`

S
(C2H50)2 P-o ~ ~ 100 I IJ
/~

( 1 9 ) ~e A 16 734 -28-0 ~9 ~ 3 T a b 1 e 5 (continued) (Phorbia ~ grub~ in the 90il) Active compound Degree of destruction in %
at an active compound con-centration of 5 ppm S

ll 51 (C;~H50)2P-O ~ ~ /
W~W 1 00 ( 3 ) (~H~i s O

( C2H5 0 ) 2P-O
~ ~ ~ N 100 ; (4) C2H5 S
(C2H50)2p 0 ~ ~ 100 ~6) / W

.

S

C~ 5 ~ fN 100 ,'~

(11 ) ~e A 16 734 _~9 lO~;g8~3 ExamE~e 6 Test insect: Tenebrio molitor larvae in the soil Solvent: 3 part~ by weight of acetone ~ulsifier: 1 part by weight o~ alkylaryl polyglycol eth~r To produoe a suitable preparation of active compound, 1 part by weight of active compound wa~ mi~ed with the ~tated a~ount of solvent, the stated amount o~ emul~ifier was added and the concentrate was diluted with water to the desired concentration.
The preparation o* active compound was intimately mixed with the soil. The concentration of the active compo~nd in the preparation was practically i~material, the only decisive factor being the amount by weight o~ acti~e compound per unit ~olume o~ soil 9 which is quoted hereina~ter in ppm (= mg/l). The 30il was ~illed into pots and the pots were left to stand at room temperature.
A~ter 24 hours the test insects were introduced into the treated ~oil and a~ter a further 2 to 7 days the degree ~0 of effectiveness o~ the active compound was determined in ~o by counting the dead and li~e test insects. The degree oi e~ectiveness was 100% i~ all the test insects had been killed and wa~ 0% if e~actly as many te~t insect3 were 3till ali~e a3 in the case o~ the untreated control.
~he active compounds, amount3 used and resulbs can be seen ~rom the table which ~ollows:

~e A 16 734 -30_ 8~3 T a b l e 6 (Tenebr:Lo molitor larvae in the soil) ctive compound Degree o~ destruction in % at an active compound concentration o:~ 5 PPm S

2 5 ~ p_o I ~ _ C2H50 ~N.3~N O
( knowrl ) /~
(B~ CH3 11 o-c4H9-se CH ~P Br o ( kIlowll ) ~ N~ N
(E ) J~J

S
(a2H5o)2P-o ~3~ 1 oo ~N N

(4) C2H5 S
(C2H50)2P-O~C1 1 00 ~ ~f'~N
- /~
(6) 3 7 I.e A 16 734 -31 - . ~;

, 10~393 ~ (continued) (Tenebrio molltor larvae in the ~oil) Active compound Degree o~ de~truction in ~ at an active compound _ concentration o~ 5 Ppm 2 5 ~ P_O_r~_ ~
/~
(11 ) C2H5 (~H3)2P-~Cl ~N ~ 100 C H -lso (13) E~amPle ?

Te~t nematode: Meloido~Yne inco~nita ~olvent: 3 parts by ~eight o~ acetone Emulsi~ier: 1 part by weight o~ alkylaryl polyglycol ether To produce a suitable preparatio~ o~ active compound, 1 part by ~eight of active compound was mi~ed with the ~tated amount o~ solvent, the ~tated amount of emulsi~isr wa~ added and the conce~trate wa8 diluted with water to the de~ired concentration.
~ he prepa~ation o~ aoti~e compound wa~ intimately mi~ed with 80il which waa heavily in~e~ted with the te~t nematodes.
~he concentration o~ the active compound in the preparation wae o~ pra¢tically ~o importance; only the amount oi active ~e ~ 16 734 -32-compound per uni^t volume o:e soi~, which i~ ~iven hereinaf~er in ppm (= mg/l), was deci~ive. ~he treatedl~oil wa~ filled into pots, let-tuce was sown in and the potslwere kept at a greenhouse temperature of 27C.
After four weeks, the lettuce roots we~e examined for infe~tation with nematodes (root galls), and the degree of effectivene~s of the active compound was determined a~ a percentage. The degree of ef~ectivene~s was 100% when infestation was completely avoided; it wa~ 0% when the infestation was exactly the same as in the ca~e o~ thè control plant~ in untreated qoil which had been in~sted in the ~ame manner.
~he active compounds, the amounts applied and the results can be ~een from the ~ollowing table:
T a b l e 7 ~ . .

Active compound De~ree o~ de~truction in % at an active compound concentration o~ ~ n~m S

Il ~O-C4Hg-sec~
3 ~ o ~ r O

(known) ~ N N
(E) S

C~3 P--O I
CH30 ~N
(~own) ~
(A) CH3 ~e A 16 734 -33-10~3~33 '~ a b 1 e 7 (continued) (Meloido~yne inco~nlta) Active compound Degree o~ destruction in % at an active compound ( a2H5 ) 2P- ~
~N N 100 (1) ,1~
C2~5 ( c2H50 ~ 2P-0 ~3 N`N ~N 1 OO
1~
(4) C2H5 E~ample 8 ~est insects~ SitoPhilus ~ranarlus 10Solvent: A¢etone 2 part~ by weight of the active compound were taken up in l,000 parts by volume o~ the solvent. The solution ~o obtained was diluted with ~urther solvent to the desired concentration~.
2.5 ml o~ the solution of the active compound were pipetted into a Petri dish. On the bottom oY the Petri dish there was a filter paper with a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount o~ active compound pèr m2 0~ ~ilter paper varied with the concentration o~ the solution o~ active compo~nd. About 25 test in~ects were ~e A 16 734 _34_ . - .

~' :

~ 9 3 then placed in ~he Petri di~h and it was covered with a ~la~
lid.
~he condition o~ the test insects wa~ observed 3 day~
after the commencement of the e~perlment~. The destruction, in %, was determined. lOO~o denotes that all test insects had been killed; Oqo denotes that no te~t inbect~ had been killed.
~he active compound~, the concentration~ of the active compounds, the test insects and the results can be seen from 1Q the following table:
T a b 1 e 8 (SitoPhilus OE~3~E39~) Active compound A¢tive com- Degree of pound con- destruct-centration ion in o~ the solution in ~o S

(C2H50)2P-0 ~ ~ 0 002 1000 (known) (B) CH3 S
( ~2H50 ) 2P-O~;~

(1~ C~5 ~

(oH30)2P-0 ~ 0.002 100 ~ .
C~
(18) ~e A 16 7:54 -35-: ' ' '. ' ,.

~O ~9 ~3 ~

T a b 1 e 8 (continued) ~Sitophilus ~ranarius) Active compound Active com- Degree o~
pound con-de~truct-~ centrationion in %
: o~ the (CH30)2P-0 ~ ~ 0.002 100 (13) C3H7-i~o 2H5 ~b~g 0.002 loo (11) C~

; (C2H50)2P-01 ~ 0.002 70 (16) . ~
: Mosquito larvae te~t Test in~ect~ ae~YPti Solvent: 99 parts by weight o~ acetone Emulsifier: 1 part by weight o~ benzylhydroxydiphenyl polyglycol ether To produce a suitable preparation oi active compound, 2 part~ by weight oi the active compound were di~olved in 1,000 part~ by ~olume oi the solvent containing the amount ; oi emul~iiier ~tated abo~e. ~he ~olution thu~ obtai~ed was diluted with water to the de~ired lower conoentration~
The aqueou~ preparation~ o~ the active compound~ were placed in glas~ ve3~al~ and about 25 moequito larvae were then placed in each gla~ v~el.

~e A 16 734 -~6-.~ ~ .- .
.: , -: .

~ 3 After 24 hours, the degree of destruction was determined as a percentage. lOO~o means that all of the larvae were killed. O~o mean that no larvaeat all were killed.
The active compounds, the concentration~ of the acti~e compound~, the test insects and the results can be 3een from the following table:
T a b l e 9 (Mosquito larvae te9t/Aede~ ~B~
Active compound Active compound Degree of concentration destruct-o~ the solution ion in (c2H5o)2-P-o-rl- ~ 0-1 100 N~N N
(known) /~J
(B) CH3 S 0.1 100 ( 2 5 )2 : N
~4) ( 2 5 )2 ~ 0.1 lO0 (1 ) ~

(C~H50)2~-0 ~ 1 ~ ~q 0.1 100 :' (6) C3~7-190 ~e A 16 734 ~37~

~, . . . .
.
, .. . . . .
: . .

9~
T a b .l ~ 9 (con-tinu~d) (lIo~quito larvae te~t/Aede~ ae~.YPti) Active compound Active compound Degree of concentration destruct of the ~olution ion in iXl ppm _ _ _ s al (C2H50)2P 0~ 0.1 100 ~1~
(2) /~
3 7 n S
( CH30 ) 2P-O~f 0 . 1 l 00 (18) ~

" Cl ( CH30)2P-~ 0.1 100 N

(13) ~
3H7-i~3o Cl 0, 1 1 00 (C2H5O) 2P-O N
C4Hg n o25\P-o~9 0.1 100 ( 1 1 ) C2H5~" Cl n~C3H7 ~ 0. l 100 (14) C2H5 ~e A 16 734 -38-~ (continued) (Mosquito lar~ae test/Aede~
Active compound Active compound Degree o~
concentration destruct-o~ the solution ion in in ~m 2 5 \ p 0 ~ 0.1 90 (15) C2~5 ~r C H O ' ~
C~l H9 -n (7) O ~1 (C2H5o)2p-o ~ 0.1 70 (16) ~he process of the present invention is illustrated by the following preparative examples.

Ex~mPle 10 ~) ~he required starting material~ could be prepared, ~or e~ample, as ~ollows:
~ ~'N~
`~ H0 1 N~

292 g o~ gaseous hydrogen chloride were pa~sed into a mi~ture o~ 99.0 g (1 mol~) oi 3-amino-pyrazolone-(5) and 600 g o~ ethanol at 20a. 119 g (1 mole) o~ 1-chlorovlny1-(2) ethyl koto~e o~ boiling polnt 39a (3 mm Hg) were then added L~ A 16 734 : -39-, . ....... . .

~ ' ~V~893 dropwise at 15 to 20 C in the ~our~e of 12 minutes. The batch was allowed -to continue to react ~lrst rOr one hour at 20 to 25C, then ~or one hour at 50C and finally for one hour with external cooling by means of ice water. The crystals for~ed were fil-tered off and rinsed with cold ethanol. The filter residue was the hydrochloride of the desired compound and was dissolved in 1.2 1 of water a~d then converted to the free compound by adding concentrated sodium hydroxide solution until the final pH value was 4. 141.2 g (86.5% of theory) of 2-hydroxy-7-ethyl-pyra~olo(1,5-a)-pyrimidine were obtained by filtration, washing and drying, in *he form of an almost, colorless powder of melting point 192-193C.

(b) ~ (IIIb) 37.5 g of gaseous chlorine were passed into a solu-tion, warmed to 70-80C, of 81.6 g ~0.5 mole) of 2-hydroxy-7-ethyl-pyrazolo(1,5-a)py~imidine in 500 g of acetic acid, while stirring, and the mixture was stirred for a further hour at 70 C. ~he crystals formed were filtered off after the mixture hs~ cooled, and were rinsed with acetic acid and then suspended in 1 1 of hot water. After having cooled, .
the product was filtered off snd was rinsed with water until the wash water no longer reacted acidically. ~fter drying, 79.6 ~ (80.6% of theory) of 2-hydroxy-3-chloro-7-ethyl-pyrazolo(l,5-a)pyrimidine were obtained in the form of a light yello~ powder of decomposition point 248 C.

., ~ ., 8~3 C ) S (,, (C7H50)2P-0- ~ (1) C H
18.7 g (0~1 mole) o~ ~,0-diethylthionophosphoric acid die~ter chloride were added dropwise to a mixture of 19.8 g (O.1 mole) of 2-hydro~y-3-chloro-7-ethyl-pyrazolo(1,5-a)pyrimi-dine, 75 ml of dimethylformamide and 15.0 g of powdered pota~sium carbonate at 20C, with stirring and ~ ht cooling, and the reaction mixture wa~ then left to react ~or a ~urther 3 to 4 hours at 20C with continued stirring, after which i~
was run9 at an internal temperature below 10C, into 200 ml o~ ice-cold ~rater. The resulting crystal~ were filtered of~, washed with water and dried. 32.4 g (93~ of theory) o~
0,0-diethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a)pyrimidin(2)-yl]-thionophosphoric acid ester were thus obtained in the form of almost co1orles~ crystals of melting point 51 to The following compound~ could be prepared ~nalogou31y:
CompoundT~ble 10 Physical data NoO Formula Omelting point, a; refractive index) 2(C2H5o)2P-o ~ 5 ~ ...
S 3H7 n 3(C2H50)2P-0 ~ 1 66 ~ N

4 (C2H5)2P-~--~ 46 ~ ~ N

~2~5 70 (C2~50)2P ~C~4Hg-n Le A 16 734 -41-~I3 6~393 r~le 10 (cont. ~

Compound Physical data No . Formule ( ~elting point, C; reIractive index ), _ _ S ql 6 (C2~0)2P-o~ 61 C3H7 i~o Br 7 C2H5 \ p 0 ~ 70 Br 8 2 5 ~p_O ~,N\~ 63 C4Hg_ i ~o 9 ( CH30 ) 2P-0 ~L 36 `N ~

Br CH30 \ p O `N~
CH30 l 2H5 ~e A 16 734 -4Z~

3 ~9893 Table 10 (cont,.) Compound Physical data No. Formula ~meltin~ polnt, C, re~ractive index) 11 2 5 ~P O C1 74 . 5 C2H5 ~N

2H5 ~ ., 12 CH30\ S ~ N~ 93 .5 / P O N~ ~

13 (CH30)2P-0 ~ 7 J3H7-iSO ~;

3 7 ~ 61.5 ~ J :, ~ 2 5 ~ p O nD3: 1.5415 N
~, '.

(This compound ~Jas isolated by extraction instead of crystallization).
am~le 11:
(C2H50)2P-0 ~ Cl (16) ~1 17,3 g (0.1 mole) of O,O-dlethyl-phosphorlc acid diester chloride were added dropwlse to a mixture of 19,8 g tO.l mole) of 2-hydroxy-3-chloro-7-ethyl pyrazolo(l,5-a)pyri~nidine, 70 ml of dimethyl~orma~lde and 11.6 g (0.115 mole) of triethyl-amine a~ an internal temperature of 20C, with stirring and external cooling, and the mixture wa~ allowed to continue to react for 3 hours at 20C. On dilution with 300 ml o~ ice-cold water, a crystalline product resulted, which was filtered o~f, washed with water and dried. 27.1 g (81.2% o~

theory) of 0,0-diethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a) pyrimidin(2)yl]-phosphoric acid ester of melting point 67.5C
were thus obtained.

Example 12.
o (C2H50)2P-0 ~ (17) ~ .' The compound w~s prepared analogously to Exa~ple 11~
but was isolated by extraction with methylene chloride instead of by crystalliæation. ~he yield was 74.5% of theory and the re~ractive index is n23: 1.5190.
Other co~pounds which can be similarly prepared include:
Table 11 Compound Mo.Formula S Cl 1~( CH30 ) 2P-O~;~N

- l~4 -:

~ con Compound ~o. ~ormula S
(C H ) p_o 3H7-n n-C4HgO \ 8 ,,~'P-CH3NH N~

21 , "~P-0 ~

3 7N~N ~ ~.

2 5 ~
' ~, ' 22 2 5 ~ p 0 Cl ~.
4HgNH /
~
,.

and the like.

It ~ill be apprecia~ed that the in~tant specification and examples are set Porth by ~ay of illustration and not limitation, and that various modifications and change~ may be made without departing from the spirit and ~cope oP the present invention.

45 ~

Claims (14)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An 0-alkyl-0-[7-alkyl-pyrazolo(1,5-a)pyrimidin-(2)yl]-(thiono)-phosphoric(phosphonic) acid ester or esteramide of the formula in which R1 is alkoxy with 1 to 6 carbon atoms, R2 is alkyl or alkoxy each with 1 to 4 carbon atoms, or alkylamino with up to 6 carbon atoms, R3 is hydrogen or halogen, R4 is alkyl with 2 to 6 carbon atoms, and X is oxygen or sulfur.

2. A compound according to claim 1, in which R1 is alkoxy with 1 to 4 carbon atoms, R2 is alkoxy or alkyl each with 1 to 3 carbon atoms, or monoalkylamino with 1 to 4 carbon atoms, R3 is hydrogen, chlorine or bromine, R4 is alkyl with 2 to 4 carbon atoms, and X is sulfur.

3. 0,0-Diethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a)-pyrimidin(2)yl]-thionophosphoric acid ester of the formula

4. 0,0-Diethyl-0-[7-ethyl-pyrazolo(1,5-a)pyrimidin- (2)yl]-thiono-phosphoric acid ester for the formula

5. 0-Ethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a)-pyrimidin(2)yl]-ethanethionophosphonic acid ester of the formula

6. 0,0-Dimethyl-0-[3-chloro-7-isopropyl-pyrazolo(1,5-a)-pyrimidin-(2)yl]-thionophosphoric acid ester of the formula

7. 0,0-Dimethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a)pyrimidin(2)yl]-phosphoric acid ester of the formula

8. A method of combatting nematodies or arthropods which comprises applying to the nematodes or arthropods, or to a habitat thereof, a nematicid-ally or arthropodicidally effective amount of a compound according to claim 1.

9. A method according to claim 8 wherein the compound is applied in admixture with an inert carrier or diluent.

10. The method according to claim 8 or 9 in which said compound is 0,0-diethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a)pyrimidin(2)yl]-thionophos-phoric acid ester.

11. The method according to claim 8 or 9 in which said compound is 0-0-diethyl-0-[7-ethyl-pyrazolo(1,5-a)pyrimidin(2)yl]-thionophosphoric acid ester.

12. The method according to claim 8 or 9 in which said compound is 0-ethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a)pyrimidin(2)yl]-ethanethionophos-phonic acid ester.

13. The method according to claim 8 or 9 in which said compound is 0-0-dimethyl-0-[3-chloro-7-isopropyl-pyrazolo(1,5-a)pyrimidin(2)yl]-thiono-phosphoric acid ester.

14. The method according to claim 8 or 9 in which said compound is 0-0-dimethyl-0-[3-chloro-7-ethyl-pyrazolo(1,5-a)pyrimidin(2)yl]-phosphoric acid ester.