CA1114378A - 2-cycloalkyl-5-hydroxypyrimidines - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention provides as new compounds the 2-cycloalkyl-5-hydroxy-pyrimidines of the general formula in which R2 represents hydrogen or alkyl, and R3 represents cycloalkyl.
The new compounds of the formula (I) are intermediates for certain phosphoric (phosphonic) acid esters and ester-amides having powerful insecticidal, acaricidal and nematicidal activity.

Description

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The invention relates to certain new 2-cycloalkyl-2-hydroxy-pyrimidines and to their use as intermediates for arthropodicides, especially insecticides and acaricides, and for nematocides.
It is known that certain 2,6-dialkyl-pyrimidin-~-yl-thiono~thiol)-phosphoric acid esters, for example 0,0-diethyl-0-(2-iso-propyl-6-methyl-pyrimidin-4-yl)-thiono-phosphoric acid ester and ()-ethyl-S-n-propyl-0-~2-iso-propyl-6-methyl-pyrimidin-4-yl)-thionothiolphosphoric acid ester, are insect-icidally and acaricidally active ~see German Patent Specification 910,652 and DE-OS ~German Published Specification) 2,360,877).
However, the action of these compounds is not always satisfactory, ?
especially if low amounts and low concentrations are used.
-~ The present in~ention is based on ~he discovery of certain new com-pounds, the 2-cycloalkyl-pyrimidin-5-yl-~thiono)~thiol)-phosphoric ~phosponic) acid es~ers and ester-amides of the general formula R3 ~/ ~ o p \ ~I~
N ~ R

` ' ' in which R represents alkyl, R represents alkyl, alkoxyl alkylthio, alkylamino or phenyl, R represents hydrogen or alkyl, R3 represents cycloalkyl and X represents oxygen or sulphur.
The new compounds of the formula ~I) are distinguished by powerful insecticidal, acaricidal and nematicidal activity.

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Preferably, in formula (I), R represents straight-chain or branched alkyl with 1 to 5 (especially 1 to 3) carbon atoms, Rl represents straight-chain or branched alkyl with 1 to 5 (especially 1 to 3) carbon atoms, straight-chain or branched alkoxy, alkylthio or alkylamino, in each case with 1 to 5 (especially 1 to 3) carbon atoms per alkyl radical9 or phenyl, X represents oxygen or sulphur, R represents hydrogen or methyl and 10R3 represents cycloalkyl with 3 to 6 carbon atoms.
The 2-cycloalkylpyrimidin-5-yl-(thiono)(thiol)-phosphoric(phosphonic) acid esters or ester-amides of the formula (I), can be prepared by a process in which a (thiono)(thiol)-phosphoric(phosphonic) acid ester halide or (thiono) phosphoric acid ester-amide halide of the general formula : IX OR
Hal P ~ Rl (II), in which R, Rl and X have the above-men~ioned meanings and Hal represents chlorine or bromine~
is reacted with a 5-hydroxy-pyrimidine of the general formula ~ N - ~ 2 (III), :-;

in which R and R3 have the above-mentioned meanings, if appropriate in the pre-

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sence of an acid acceptor and, if appropriate, in the presence of an inert diluent.
The present invention thus provides, as new compounds, 2-cycloalkyl-5-hydroxy-pyrimidines of the formula R ~/ ~ 0~ ~III) : N R2 `:
: in which ~; R is hydrogen or alkyl, n R is cycloalkyl.
Surprisingly, the 2-cycloalkyl-pyrimidin-5-yl-(thiono)~thiol)-phosphoric(phosphonic) acid esters and '' . -2a-'';

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-3--ester-amides according to the invention exhibit a better inqecticidal, acaricidal and nematicidal action than the corresponding compounds, known from the prior art, of analogo~s structure and o~ the same type of action~
If, for example, 2-cyclobutyl--5-hydroxypyrimidine and O-ethyl-ethanephosphonic acid ester chloride are used as starting materials, the reaction can be outlined by the following equation:
, ~ -OH + Cl-P \ 2 5 , ~ 0~3 o p, 2 5 : . ~
The (thiono)(thiol)-phosphoric(phosphonic) acid ester : halides and (thiono)-phosphoric acid ester-amide halides to be used as starting materials, are defined by the formula (II).
. Preferably in this formula, R, Rl and X have the : 15 meanings statPd to be preferred in connection with the formula (I) and Hal represents chlorine.
The (thiono)(thiol)-phosphoric(phosphonic) acid ; ester halides and (thiono)-phosphoric acid ester-amide - halides of the formula (II) are known compounds. The Following may be mentioned as examples: û-methyl~, O-ethyl-, O-n-propyl-, O-iso-propyl-methane-, -ethane-, -propane- and -phenyl-phosphonic acid ester chloride and the corresponding thiono analogues; O,O-dimethyl-, O,O-diethyl-, O,O-di-n-propyl, O-methyl-O-ethyl-, O-methyl-O-n-propyl, O~methyl-O-iso-propyl, O-ethyl-O-n-propyl-. and O-ethyl-O-iso-propyl-phosphoric acid diester chloride .:~ and the corresponding th.ono analogues; O,S-dimethyl-, O,S-diethyl-, O,S-di-n-propyl-, O,S-di-iso-propyl-, -O-ethyl-S-n-propyl-, û-ethyl-S-iso-propyl-, O-ethyl-S-~e A 19 039 ~ .;. .:

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sPc.-butyl-, 0-n-propyl-S-ethyl-, 0-n-propyl-S-iso-propyl-and 0-iso-propyl-S-n-propyl-thiolphosphoric acid cJiester chloride and the corresponding thiono analoguas; and 0-methyl-N-methyl-, 0-methyl-N-ethyl-, 0-methyl-N-propyl-, 0-methyl-N-iso-propyl, û-ethyl-N-methyl-, 0-ekhyl-N-ethyl-, 0-ethyl-N-n-propyl-, 0-ethyl-N-iso-propyl-, 0-n-propyl-N-methyl-, 0-n-propyl-N-ethyl-, 0-n-propyl-N-n-propyl-, ;~
0-n-propyl-N-iso~propyl-, 0-iso-propyl-N-methyl-, 0-iso-propyl-N-ethyl-, 0-i~o-propyl-N-n-propyl- and 0-iso-propyl-N-iso-propyl-phosphoric acid ester-amide chloride and the corresponding thiono analogues.
` The 5-hydroxy-pyrimidines also to be used as starting materials are deFined by the formula (III). Preferably in this formula, R2 and R3 have the meanings stated to be preferred in connection with formula (I)~
The following may be mentioned as specific examples:
2-cyclopropyl-5-hydroxy-pyrimidine, 2-cyclobukyl-5-hydroxy-pyrimidine, 2-~cyclopentyl-5-hydroxy-pyrimidine, 2-cyclohexyl-5-hydroxy-pyrimidine, 2-cyclopropyl-4-methyl-5-hydroxy-pyrimidine, 2-cyclobutyl-4-methyl-5-hydroxy-pyrimidine, 2-cyclopentyl-4-methyl-5-hydroxy-pyrimidine and 2-cyclohexyl-4-methyl-S-hydroxy-pyrimidine.
The 5-hydroxy pyrimidines of the Formula (IIl) are new compounds. They are obtained when amidine hydro-chlorides of the general formula -, !. 3 ~NH2~ C1~3 ( I V ), in which R3 has the abovementioned meaning, are reacted with acrolein derivativesof the general formula - R2 (y)~ ' (CH ~ 2N--C=C-CHO

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in which R2 has th~ abovementioned meaning, in the presence of a base, for example 60dium metl-ylate, ` and, if appropriate, in the presence of a diluent, for - 5 example methanol, at temperatures between 0 and 100C, and thereafter, following addition of excess aqueous potassium hydroxide solution, the mixture is heated for several hours in an autoclave to 1~0 - 200C. To work up the mixture, it is concentrated,diluted with a small amount of water and brought to a pH value af betwean 4 and 5. The products of the formula (III) are hereupon `~ obtained in a crystalline form.
Amidine hydrochlorides of theformula (IV) are known compounds (see U.S. Patent Specification 4,012,506). The following may be mentioned as examples: cyclopropyl-amidine hydrochloride, cyclobutylamidine hydrochloride, cyclop~3ntylamidine hydrochloride and cyclohexylamidine hydrochloride.
Acrolein derivatives of the formula (V) are also 20 known (see Archiv der Pharmazie 300 (1967), 704-70e).
The following may be mentioned as examples of these: 2-methoxy-3-dimethylamino-acrolein and 2-methoxy-3-dimethyl-amino-3-methyl-acrolein.
The process for the preparation of the cycloalkyl-pyrimidin-5-yl-(thiono)(thiol)-phosphoric(phosphonic) acid esters and ester-amides according to the invention is preferably carried out in the presence of a suitable solvent or diluent. Virtually any of the inert organic solvents can be used for this purpose,especially aliphatic and aromatic, optionally chlorinated, hydro-carbons, such as petrol, benzene, toluene, xylene, methylene chloridej chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene; ethers 9 such as diethyl ether,dibutyl ether, tetrahydrofuran and dioxan;
-~ 35 ketones, such as acetone, methyl ethyl ketone, mekhyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such as acetonitrile and propionitrile.
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Any of the cu6tamary acid-binding ag~nts can be used as acid acc~ptors. Alkali metal carbonatos and alkali metal alcoholates, such a~sodium carbonate and potassium carbonate, sodium methylate and ethylate and potassium S methylate and ethylate, have provlsd particularly suitable for this purpos~, as havs s31iphatic, aromatic or hetero-cyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylam:ine and pyridine.
The raaction temperature can be varied within a substantial range. In gen~ral, the reaction is carried out at from 0 to 80C, pr~tferably at from 20 to 60C.
;~ The process aecording to the invention is in general carried out under normal pressure.
The starting materialE; are usually employed in equimolar amount~ for carr~ing out the process according to the invention. As excess of one or other reactant - brings no significant advantages. The reaction is in general carried out in a suitable diluent in tha presence of an acid acceptor, and the reaction mixture i~ stirred for several hours at the required temperatur~. Thereafter, an organic solvent, for example toluene, is added and the organic phase is worked up in the usual manner by washing, drying and distilling off the solvent.
The new compounds are obtained in the ~orrn of oils, which in part cannot be distilled without decomp~sition, but are freed from the last volatile constituents by so-called "incipient distillation", that i9 to say by prolonged heating under reduced pressure to moderately elevated temperatures, and are purified in this manner.
They are characterised by the refractive index.
The active compounds are well tolerated by plants, have a ~avourable level of toxicity to warm-blooded animals, and can be used for combatin~ arthropod pests, especially insects and acarids, and nematode pests which are enco~ntered in agriculture, in forestry, in the pro~

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~ection Or stored pro~ucts and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and a~ainst all or some stages of development. The abovementioned pests include:
from the class of the ~sopoda, for exa~ple Oniscus asellus, Armadillidium~ul~re and Porcel'lio s'cab'er~
from the class of the )7iplopod-; for example Blaniulus ~_ttulatus, from the class of the C ~ la, for example Geophilus carpopha~us and Scuti~ spec.
: from the class of the ~ a, for example Scuti-~; ~erell_ immaculata;
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from the order of the Thysanura, for example Lepisma saccharina, , from the order of the Collembola, for example . _ .. .... _ ~ .
Onychiurus' a'rm~us;
from the order of the ~Fthoptera~ for example Blatta orientalis, Peri~lan~ta americana, Leuco~haea ~ _., .. , . . . .__ ... . _..
maderae, Blattella germanica, Acheta domesticua, Gry'l'lo-talpa spp., Lo:custa ~ ria mig~a'torioides, Melanop~usdifferentialis and Schistocerca ~
. from the order of the DermaPtera, for example :~' 'Forficula auricularia; . ~' -`- from the order of the ~ , for example ~ ' - 25 Reticulitermes spp.;
.
from the order of the A:noDlura, for example Phylloxera vastatrixg ~ spp., Pediculus humanus ':
corporis,- Haematopinus spp. and ~ spp.;
. ._ '~. rrom the order of the ~lallopha~a, for example .~............. 30 Trichodectes spp. and ~a~ali:nea spp.;
._ ~ , ~ _ ~rom the order of the Thysa~optera~ for example Hercinothrips femoralis and Thrips tabaci-from the order of the Het'e~optera, for example .~ spp., Dysdercus interme~ius~ Pies~a quadrata, . 35 Cimex lectula~ius, Rho~ius'prol'iXus and Triatoma spp.;
: ~rom the order of the Homoptera, for example ; ,;

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vaDora~iorum, Aphis~ gos's'yp'ii ,' 'Bre~i'c'o~ne''b'r'a's's'i'c'ae~
Cr~ptomy-zus ribis~ Doral~is~ fa~b~ae,~ ~o~ra~is'p~o~mi,~ E~losoma lani~ rum, Hyaloo`t'erus'a~undin'is,' ~ ~a~e~n~ae, Myzus spp., Phorodon humuli, Rhopalo~si'~hu~ p~adi,' Empoasca spp , Euscelis blIobatus,''Ne~h'o't'e't't'iX' ~ , Lecanium corni,~ Saissetia'oleae,'Lao'd'e' ~ 'strlatellus, Nila~arvata lu~ens, Aonidiella aurantii, Aspidiotus . .
hederae, Pseudoco~cus spp. and ~ lla spp.;
from the order of the'LeDido~tera, ~or example Pectinophora ~ossypiella, ~u~alus piniarius,~ Cheimatobia .~ -bru~ata Lithocolletis-blancardel'la,''Hyponoffle'uta' ~ , Plutella maculipennis,' Malacosoma n'eust'~ia, Eupro'c't'is : chrysorrhoea, Lymantria spp., Bucculatrix thurheri'ella, Phyllocnistis cit.ella, Agrotls spp., Euxoa spp., Feltia . spp., Ear~as insulana, Heliothis spp.,' Laphy~ma eXi~ua, ~ Mamestra brassicae, Panolis ~lammea, Prodenia lit'ura, ._ . . . , . . .. , _ Spodoptera spp.,''Trichoplusia ni,''Carpocapsa pomonella, Pieris spp., Chilo spp.,'P~rausta nubilalis, Eph'estia kuehniella,'Galle'ria mel'l'onella,''Cacoe'cia p'od'ana, Capua _,, , . . ~".,__ __ _ _ . . _ , .
'' reticulana,~Choristoneura fum _erana, Clys'ia' ~ , Homona rna~nan rna and Tortrix vi'ridana;
. ~ , _ :. ~rom the order of the'Cole'optera, for example . Anobium punctatum? Rhizopertha' dom , Bruchidlus obtec us, Acanthoscelid^s obtectua, ~ b'aj'ulus, A~elas_ica alni, Leptinotarsa decemllneata,''P'h'aedon ~ cochleariae, Diabrotica spp.~ ~ ch'r'y'soce~hala, Epilachna _a'rives_is, At'omaria spp.,' ryzaephilus : surinamensis, Anthonomus spp.,' Sitop'hilus spp., Otiorrhynchus~ sulcatus~ Cosr~o:polites sordidus, Ceuth'orr-: ' hynchus assimilis, ~ po's't'i'ca,''D'e'~r~e's'tes spp. 5' Tro~o-. _ . derma spp., Anthren'us spp.,'' ~ spp.,''Lyc'tus spp., ,, .__._ -- -M ~ aeneus,' Pti'~us spp.,'Niptus'ho'l'o'l'eucus, ~' Gibbium ps'yllo:i'des,''T~ibolium spp.,~ Te~ebrio rnolitor, ~riotes spp., Conoderus spp.,~ Melolontha ~elolontha, ;
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Arrl~hir.~allon's'ol's't'it'i'alis an~ Cost'e'~'tra''z'eaIa'n'~i'c~;
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from the order o~ the Hymen'opte'ra, for example DiDrion spp., ~lop'locam~a spp.,~L'asi'us spp.,' ~onc~o'r'i'um pharaonis and~'Ves~a spp.;
. . . _ from the order of the''DiD't'e'ra, for example' A~ed'es spp., Anopheles spp., Culex spp.,' ~ hi'la' me'~no~as't'er,''M~sca spp., Fannia spp.,' Cal'li~h'ora'~ ~ ,''Lu'c'i'l'ia spp., Chrysom~Jia spp., Cuterebra spp.,''Gastrop'hi'l'us spp., Hyppobosca spp.,~t~ spp. J' Oestrus spp.,'' ~
spp., Tabanus sppO,' Tannia spp., Bibio'hor_'ul'an'us, ~scinella frit~ Phorb'ia spp., Pe~om~ia ~ ~ g Ceratitis c_ 1~ a, ~ ~ . .
I . Dacus oleae and Tipula paludos~
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from the order of the 5iohonaptera, for example ~ c'h'eoPis and Ceratoohyllus spp.;
from the class of the-Arachnida, for example Scor~io maurus and Latrodectus 'mac't'ans ..... __, , from the order of the Ac~lrina, for example A'carus siro, Ar~as spp.,''Ornithodoros spp., Dermanyssus ~allinae, - Eriooh~es' ribis,'Phyllocootruta~oleivora,'~Boooh'iIus spp., Rhi~lce~halus spp.,' Amb'lyomma spp-,' Hyalomma spp.,~IXodes spp., Psoroot'es spp.,'Choriopte~s spp.,''Sarc~ spp., Tarsonemus spp., Bry'obia oraetiosa,'Pa'n'o'n~c'hus spp. and ''~ Tetranychus spp _ ___ .
. The plant-parasitic nematodes include' spp., Radopholus'similis, semipenetrans, Heterode'ra spp.~' ~ spp., Aph'eIen-_ _ _ _ _ . . . _ . _ _ _ choi-des spp., ongidorus spp.,'' ~ spp., and Trichodorus spp..
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders,-dusting agents~ :
: foams, pastes, soluble powders, granules, aerosols, sus-pension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, .::
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coating co~lpositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and ~umigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner, : for example by mixing the active compounds ~ith extenders, that is to say liquid or lique~ied gaseous or solid diluents or carriers, optionally with the use of surface-active agents~ that is to say emulsifying agents a~d/or dispersing agents and/or foam-forming agents. In the case of the use Or water as an extender3 organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons~ such as cyclohexane or paraf~ins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methy] ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
:
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane~
nitrogen and carbon dioxide.
; 30 As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quart~, attapulgite, montmorillonite or diatomaceous earth, and ground synthe'Gic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and ~ractionated natural rocks such as calcite~ marble~ pumice, sepiolite . . , ~ Le A 19 039 ..

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and dolomite, as wel} as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells~ maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there~
may be used non-ionic and anionic emulsifiers~ such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers~ for example alkylaryl polyglycol ethers~
alkyl sulphonates, al'cyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, li~nin sulph:ite waste liquors and methylcellulose.
Adhesive3 such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcoho.L 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 or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
; The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention may be used in the form of their formulations of the types that are commercially available or in the use forms prepared from these formulations.
The acti-re compound content of the use forms pre-pared from the formulations of the type~ that are com-mercially ava;lable can vary within wide ranges. ~heactive compound concentration o~ the use forms can be from 0.0000001 to 100% by weight of active compound, -~ preferably from 0.01 to 10% by weight.
The compounds may be employed in a customary manner , ' ~-':

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appropriate for the particular use forms.
'~hen used against pests harm~ul to health and pests o~ stored products, the active compounds are distlnguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.
The 2~cycloalkyl-pyrimidin-5-yl-(thiono)(th~l)-phosphoric(phosphonic) acid esters and ester-amides also have a good root-systemic action against sucking and biting insects and mites.
The present invention also provides an arthropodicidal or nematicidal composition containing as active ingredient a cornpound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating arthropods (especially insects or acarids) or nematodes which comprises applying to the arthropods or ne~atodes , or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present . invention in admixture with a diluent or carrier. ;~
The present invention further provides crops protected from damage by arthropods or nematodes by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention ' was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
3 The pesticidal activity of the compounds of this invention is illustrated by the following biotest Examples.
In these Exz.mples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
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Example A
Critical concentration test/soil insects Test insect: Phorbia antia~ua grubs in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 par~ by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight Or active compound was mixed with the stated amount Or solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was practically imrnaterial, the only decisive factor being the amount by weight Or active compound per unit volume o~ soil, which is ; quoted hereinafter in ppm (~ mg/l). The treated soil ; was filled into pots and the pots were left to stand at room temperature.
After 24 hours the test insects were introduced into the treated soil and àfter a further 2 to 7 days the degree of effectiveness of the active compound was determined in % by counting the dead and the live test insects. The degree of effectiveness was 100%
if all of the test insects had been killed and was 0%
if exactly as many test insects were still alive as in the case of the untreated control.
In this test, for example,the following compounds showed a superior action compared to the prior art: (7) and (l6?.
Example B
Critical concentration test/soil insects Test insect; Tenebrio molitor larvae in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight Or alkylaryl polyglycol ether Le A 19 039 ,.. ~, . . ..
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To produce a suitable preparation of actlve compound, 1 part by weight of active compound was mi~ed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation Or active compound was intimately mi~ed with the soil. The concentration of the active compound in the prepa~ation was practically im~2terial, the only decisive ractOr being the amount by weight of active compound per unit volume of soil, which is quoted hereinafter in ppm (= m~/l). The treated soil was filled into pots and the pots were left to stand at room tempera-ture.
After 24 hours the test insects were introduced into the treated soil and after a further 2 to 7 days the degree of effectiveness of the active compound was determined in % by counting the dead and the live test insects. The degree of effectiveness was 100% if all of the test insects had been killed and ~as 0% if exactly as many test insects were still alive as in the case of the untreated control.
In this test~ for example, the following compounds showed a superior action compared to the prior art (1), -~ ~ll) and (7).
~
Critical concentration test/root-systemic ~ction Test animal: ~ persicae . ~
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 we~ght of active compound was mixed with the stated amount of solvent, the stated amount Or emulsifier ~- was added and the concentrate was diluted with water ~; 35 to th~e desired concentration.

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The preparation Or active ~ompound was intimately mixed with the soil. The concentration of the active compound in the preparation was o~ practically no im-portance; only the amount of active compound per unit volume o~ soil, which is given hereinafter in ppm (=
mg/1), was decisive. The treated soil was filled into pots and these were planted with cabbage (Brassica oleracea). The active comoound could in this way be taken up rrom the soil by the plant roots and be trans-ported into the leaves.
To demonstrate the root-systemic effect, only the leaves were infested with the above-mentioned test animals after 7 days. After a further 2 days~ the results were evaluated by counting or estimating the dead animals.
The root-systemic action of the active compound was deduced from the destruction data. It was 100% when all of the test animals had been killed and 0% when just as many test insects were still alive as in the case of the un-treated control.
In this test, for example, the following compounds showed a superior action compared to the prior art: (4) and (5).
Exam~le D
.
' Critical concentration test~root-systemic action ' 25 Test insect:'Phaedon' c'ochleariae larvae Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation of active compound was intimately mixed with the soil. The concentration Or the active .'~ . .
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r j 1~ -compound in the preparation was of practically no im-portan~e; only the amount Or active compound per unit volume of soil, which is given hereinafter in ppm (~
mg/l)~ was decisive. The treated soil was filled into pots and these were planted with cabbage (Brassica; ole-racea). The active compound could in this way be taken up from the soil by the plant roots and be transported into the leaves.
To demonstrate the root-system~c effect, only the leaves ~ere infested with the above-mentioned test animals after 7 days. After a further 2 days, the results were evaluated by counting or estirnating the dead animals.
The root-systemic action of the active compound was deduced from the destruction data. It was 100% when all of the test animals had been killed and 0% when just as many test insects were still alive as in the case of the untreated control.
In this test, for example, the following compounds showed a superior action compared to the prior art: t4) ; 20 and (5).
Exam~le E `
Critical concentration test/nematodes Test nematode: Meloido~ne inco~nita Solvent: 3 parts by weight of acetone Emulsifier: l part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, l part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation of active compound was intimately mixed with soil which was heavily infested with the test nematodes. The concentration of the active compound in the preparation was o~ practically no importance;

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1~ -only the amount of active compound per unit volume of soil, which is given hereinafter in ppm (- mg/l), was decisive. The treated soil was filled into pots, lettuce was sown in and the pots were kept at a greenhouse 5 temperature of 27 de~rees C.
After 4 weeks, the lettuce roots were examined for infestation with nematodes (root galls~, and the degree of effectiveness of the active compound was determined as a percentage. The degree of effectiveness was 100% when infestation was completely avoided; it -j was 0~ when the in~estation was exactly the same as in the case of *he control plants in untreated soil which had been infested in the same manner.
In this test, for example~ the following compounds showed a superior activity compared to the prior art: (4) and (5).
; ExamDle F
LD100 test Test animals: S_to~hilus granarius Number of test animals: 25 Solvent: Acetone The active compound was taken up in the solvent at a rate of 2 g per litre. The solution so obtained was diluted with further solvent to the desired con~
centrations~ , ;
2.5 ml of the solution of the active compound were pipetted into a Petri dish. On the bottom of the Petri dish there was a filter paper with a diameter of about 9.5 cm. T~e Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per square metre of filter paper varied with the concentration of the solution o~ active compound.
The stated number of test animals was then placed in the Petri dish and the dish was covered with a glass lid.
~ The condition of the test animals was observed 3 days after the commencement of the experiments. The -. ~ , ~ Le A 19 039 , destruction, in ~, was determined. 100% denoted that all o~ the test animals had been killed; 0~ denoted that none of the test animals had been killed.
In this test, for example~ the following compounds showed a superior action compared to the prior art: (4) and (6).
Example G
La~h~ test - Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) were treated by beirlg dipped into the preparation of` active compound of the desired concentration and were infested with cater-pillars of the owlet moth ( ~ fru~iperda), as longas the leaves were still moist.
After the specified periods of time, the destruction in % was determined. 100~ meant that all of the cater-pillars had been killed whereas 0% indicated that none af the caterpillars had been killed.
In this test~ for example, the following compounds ~howed a superior activity compared to the prior art:
(13), (4)~ (1), (7) and (16).
Example H
~ test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether ~o produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with .~ .
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~he stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with wate-to the desired concentration.
Bean plants (Pha's s ~ ris) which were heavily infested wlth the two-spotted spider mite'~' urticae) in all stages of development were treated by being dipped into the preparation of the active compound of the desired concentration.
After the specified periods of time, the degree of destruction was determined as a percentage: 100%
meant that all of the spider mites were killed whereas 0% meant that none of the spider mites were killed.
In this test, for example, the following compounds showed a superior activity compared to the prior art:
'` 15 (13), (4), (7) and (5).

Example 1:
S
~3-o-P(oc2H5)z (1) .; . .
;' A mixture of 300 ml of acetonitrile, 17.8 g (0.1 mol) 20 of 2-cyclohexyl 5-hydroxy-pyrimidine, 20.7 g (G.15 mol) of potassium carbonate and 18.8 g (0.1 mol3 of 0,0-diethyl-thionophosphoric acid diester chloride was stirred for 2 hours at 45C. The reaction mixture was then poured into 400 ml of toluene and was washed with twice 300 ml of water.
The toluene solution was dried over sodium sulphate and evaporaSed i vac'uo. The residue was subjected to in-cipient distillation in a high vacuum. This gave 21.7 g (66~ of theo~y) of 0,0-diethyl-0-~2-cyclohexyl-pyrimidin-5-yl}thionophosphoric acid ester in the form of a brown oil - ~ of refractive index n23: 1.5158.
The following compounds of the formula ~ .

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The 5-hydroxy-pryimidines to be employed as starting materials could be prepared, for example, as follows:
Example a:
o~s 83,8 ~ (0.65 mol) of 2-methoxy-3-dimethylamino-acrolein (for preparation see H.Plumpe and E. Schegk, Archiv der Pharma2ie 300, (1967) pages 704-708) were added : . at room temperature to a mixture of 116.2 g (0.7~ mol) of cyclohexylamidine hydrochloride, 150 ml of methanol and 0.8 mol of a solution of sodium methylate in methanol.
The mixture was boiled for 5 hours under reflux and cooled to room temperature, and the salt which had precipitated ~ was filtered of~. It was rinsed with 100 ml of methanol, - a solution of 56 g (1 mol) of potassium hydroxide in 100 ml . ~5 of water was added to the filtrate and the solution was `~. then heated in an autoclave for 4 hours to 190C. The ~ methanol was then distilled off in ~acuo, 50 ml of ice .:~ water were added to the residue and the solution was brought : to a pH value of 4.5 by adding concentrated hydrochloric acid, whilst cooling; After 30 minutes, the product which had crystallised out was filtered off and 96 g (83% of theory) of 2-cyclohexyl-5-hydroxy-pyrimidine were thus obtained as a pale brown-coloured crystal powder of melting point . t, 163C
: 25 The following compounds o~ the formula : ~3 ~ ~ _ ~ ~2 (III) ~ ' ' could be prepared analogously:

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Claims (5)

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

1. A 2-cycloalkyl-5-hydroxy-pyrimidine of the formula (III) in which R2 is hydrogen or alkyl, and R3 is cycloalkyl.

2. A compound according to claim 1, in which R2 is hydrogen or methyl, and R3 is cycloalkyl with 3 to 6 carbon atoms

3. 2-Cyclohexyl-5-hydroxy-pyrimidine.

4. 2-Cyclopropyl-5-hydroxy-pyrimidine.

5. 2-Cyclopentyl-5-hydroxy-pyrimidine.