Note: Descriptions are shown in the official language in which they were submitted.
~fi~7~ ~
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.
,,.' , ' ' '.. ' ' , : ~ ' .
a~ ~ ~
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-
-2-
'' '
.. . .
,
.
. , , . . . ~ '.
.
.
r'~-~`
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-
'';
.
~. . - , , , . , : - , :- . ` . :
. .
-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
~ .;. .:
': t ' "'
~''~"' ' ' "' , ' , ' '
, ,
- y - ~
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 ),
NH2
in which
R3 has the abovementioned meaning,
are reacted with acrolein derivativesof the general formula
- R2 (y)~ '
(CH ~ 2N--C=C-CHO
OCH3
.
Le A 19 039
.... . .
,"
,.' ' ' '
~, ' ~ . ' .
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.
. . ,
'. .
~ ~ Le A 19 039
. `1
..
... . .
.: ' ' : ~.: ' ' ~
: ~ :
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~
.
,'
,
-1 L~ A 19 39
:~ '
~.. ,.. ~ . ` :
. : .. , . . .: .
~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;
s ~
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
; ,;
;. :
~: Le A 19 039
.s
. : - ,
~,
: '. . :. ,
Aleurodes b~assic'ae,' ~emisia't'a'b'aci,' ~ria'Ie'u~o'des
__.,_ ., . .. ~ _ .. ... .... ....
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,
;
. .
~ Le A 19 039
.:.....
' ~ ;
. . .. . .
: :~ ~ ' . ~ ' .
Arrl~hir.~allon's'ol's't'it'i'alis an~ Cost'e'~'tra''z'eaIa'n'~i'c~;
.. _ ...... . , ., .,, ,, ., .. . _ . . . .. _ _ .
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~
.. ., _ .
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,
.::
. .
~ Le A 19 039
: :
-
~; :
:
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
..
. ., - . ,, , : .,
:. , :
'' ~
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
, ' ~-':
. .
Le A 19 039
.. . . . .
:
b' ~
._ , , _ .
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.
. .
,
.
"
~i Le A 19 039
~,..... . .
~,,
;'
,~, ,~, . ... . . . .
; ' , ` ': : ~ ~ .
~ .
.
3 7~
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
,.. ~, . . ..
. , ., , ,:
.
~ .
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.
: .
Le A 19 039
:~
... . .
,
,.
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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. . .
.:
: ~ : ' ", ' ' " '~ `
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r j
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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;
Le A l9 039
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.
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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 -
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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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could be prepared analogously:
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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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Example R2 R3 Yield Me l~in~s point
(~ Of ( C~
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b ~1 ~ E15 1~7
c H n
..
.~ d D 67 2~0
:; ~ CX3 a ~
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