CA1050553A

CA1050553A - Novel 1,2,3-triazolyl phosphorus compounds

Info

Publication number: CA1050553A
Application number: CA208,605A
Authority: CA
Inventors: Beat Bohner; Dag Dawes; Haukur Kristinsson; Willy Meyer
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1973-09-10
Filing date: 1974-09-06
Publication date: 1979-03-13
Also published as: AT329319B; NL7411956A; FR2243205A1; JPS5053536A; DE2442843A1; EG11441A; ATA723274A; AU7310974A; GB1481867A; IL45624A0; IL45624A; FR2243205B1

Abstract

Abstract of the Disclosure New 1,2,3-triazolyl phosphorus compounds, their manufacture and use as active ingredients for controlling insects, representatives of the order acarina and phytopathogenic nematodes.The compounds correspond to the formula

Description

The present invention relates to 1,2,3-triazolyl compounds, to processes for their prepara~ion and to their use for the control of pests.

The said 1,2,3-triazolyl compounds correspond to the formula X
¦¦~ R
N = C - O - P
R3 - N ¦ \ R2 ~I) \~ = C - Y
()n wherein Rl represents alkyl, alkoxy, alkylthio9 alkoxyalkylthio, amino, monoalkylamino or dialkylamino, R2 represents alkoxy, alkylthio, amino, monoalkylamino or dialkylamino, I R3 represents unsubsti$uted phenyl, or pheny~l mono- to tri- substituted, : 10identically or differently, by fluorine, chlorine, bromine and/or :,iodine or mono substituted by methyl "nethoxy or trifluoromethyl, Y represents hydrogcn, chlorine or bromine, n represents the numbers O or 1, and X rep~esents oxygen or sulphur.
: ~The present inven~ion also relates to a process for the preparation of compounds of the formula I comprising reacting a compound of the formula . ~ .
X
~ 1/ p _ Hal '~, R2 with a compound of the formula HO - C C - Y

\ N / n ,I R3 ~, ~

: (~ 7i :, ...

. . .

in the presence of an acid binding agent, or with a compound of the formula MeO - C ~ C - Y
., 11 11 . N \ / N~~~)n IN

.; :
wherein Rl to R3, X, Y and n have the meanings given above, Hal stands for fluorine, chlorine, bromine or iodine, and Me stands for a monovalent metal.
The alkylg alkylamino, dialkylamino, alkoxy, alkylthio and : alkoxyalkylthio groups denoted by Rl and R2 can be branched-chain or straight-chain, substituted or unsubstituted, and they have 1 to 18, especially, however, 1 to 5, carbon atoms in the chain, Substituents on these groups are preferably: fluorine, chlorine, methoxy, methylthio and/or nitro. Examples of such groups are, inter alia: methyl, methoxy, ethyl, ethoxy, ethylthio, methylamino dimethylamino, .

~ i -~ ", , , :; , .

.
', .

~....

':~'. ' , ' ~

. , .

~ 2a -,, .: : .

methoxymethylthio, methoxyethylthio, e~hoxyethylthio, n-propyl, n-propoxy, n-propylthio, isopropyl, isopropoxy, isopropylthio, n-, i-, sec.-, tert.~butyl, n-pentyl and isomers thereof, n-pentoxy, n-pen~ylthio and chloromethyl.
Substituents of the phenyl groups in the case of R3 are, for example, one or more identical or different fluorine, chlorine, bromine and/or iodine atoms, alkyl, haloalkyl, cyano, alkoxy, nitro~ alkoxycarbonyl, alkylthio, alkylsulphonyl, alkylsulphinyl, acetylamino, amino, monoalkylamino 9 dialkylami.no, phenoxy and/or phenyl-sulphonyl groups.
Compounds of formula I which are preferred on account . of their action are those wherein ~ .
: Rl represents Cl-C5-alkyl, Cl-Ccj-alkoxy, C3-C5-alkylthio, -methylamino or dimethylamino,, R2 represents Cl-C5-alkoxy ox dimethylamino, R3 represents unsubstituted phenyl, or phenyl mono- to - trisubstitu~ed, identically or differently, by fluorine, chlorine, bromine and/or iodine, or mono-substituted by methyl, methoxy or trifluoromethyl, ~ Y represents hydrogen, chlorine or bromine, ; n represents the numbers 0 or 1, and X represents oxygen or sulphur.
Particularly preferred compounds of formula I are 25 those wherein _ 3 _ , . . .

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

. Rl represents methyl, ethyl, methoxy, ethoxy, C3~C5-alkylthio~ methylamino or dimethylamino, R2 represents methoxy, ethoxy or dimethylaminog R3 represents unsubstituted phenyl, or phenyl mono- to 5 trisubstitwted by fluorine, chlorine and/or bromine : or monosubstituted by methyl, methoxy or tri~luoromethyl, Y represents hydrogen, chlorine or bromine~
n represents the numbers O or 1, and X represents oxygen or sulphur.
More especially preferred compounds of formula I
. are those wherein Rl represents methoxy, ethoxy or n-propylthio, R2 represents methoxy or ethoxy, . ., .~ R3 represents unsubstituted phenyl, or phenyl mono- to , ~ .
trisubstituted by fluorine, chlorine and/or bromine . or monosubstituted by methyl, methoxy or trifluoromethyl, Y represents hydrogen, chlorine or bromine, n represents the numbers O or 1, and X represents sulphur.
, . ..
. ..
, ~ ; ~ .' . . I .
:::

... :' ':

~ 4 ~

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

55~3 .
The compounds of formu~a I can be Drepared by the following .methods known per se:

X

; la) l > P~Hal ~, EO-C C-~ acid binding >
R2. Il 11 agent (II) ~ /N ~ (O)n - '.-R3 (III) ; . . ' ' . ' ' ' ., : ' . X
R \ 11 lb) 1 >P-Hal ~ MeO~ -Y
R2~ . Il 11 . --~ I
(II ? ~ N/

(IV) ', . 3 : ~ . X ' . . ` .
2a) Rl\~Ha~ ~y I 11 Il . acid binding ~ -. Xal ~ ~ ~ (O)n agent (V) . ¦ (III3 - 3 ~VI :
.,: X , .. . . / ..
~b) l \ P~Hal + MeO~ Y
11 11 . ' : . ~V) N~ /N-~O)n ~
, ¦ (IV) ~ :
;~ X 3 l~ 11 ~ R H _ id bi -~ -Y . 2 agent .¦ 11 11 ~VII) ~al N ~ ~ (O)n (VI) I ~ R2Me (VIII) . 3 .
~: ' ' ' ", , ' '' :, .' .. . . : .
, ' ' ' ' ' ' ' ' , ' ' ~ ' ~ ' ,, , S

~: :

~ S~ 5 5 3 In formulae II to VIII, the symbols Rl to R3, X, Y
and n have the meanings given for formula I, Hal stands for fluorine, chlorine, bromine or iodine, particularly, however, for fluorine, chlorine or bromine, R'2 stands for alkoxy or alkylthio, and Me denotes a monovalent m~al, preferably an alk~li metal, especially sodium or potassium.
Suitable acid-binding agents are, for example, the following bases: tertiary amines such as triethyl~lne, dimethylaniline and pyridine, inorganic bases such as hydroxides and carbonates of alkali metals and alkaline-earth metals, preferably sodium and potassium carbonate.
The reactions la, lb, 2a and 2b are performed under normal pressure, at a temperature of 0 - 150C, and preferably i in solvents or diluents which are inert to the reactants.
Suitable solvents or diluents are 5 for example: aromatic hydrocarbons such as benzene, toluene and li~roins~
halogenated hydrocarbons such as chlorobenzene, polychloro-benzenes and bromobenzene; chlorinated alkanes having 1 to 3 carbon atoms; ethers such as dioxane and tetrahydro-f-~ran; esters such as acetic acid ethyl ester; ketones such ;
as methyl ethyl ketone and diethyl ketone; and nitriles, etc Of the compounds of formula III or IV to be used as starting materials, only 2-phenyl-4-hydroxy-1,2g3-- triazole is kno~l. This is prepared by firstly converting glyoxal, by reaction with phenylhydrazine, into glyoxal-diphenylhydraæone, and condensing this in the presence of copper sulphate to 2-phenyl-1,2,3-triazole :

'- , ., , . ' :

(see J.L. Riebsomer, J.Orgc Chem. 13, (1948)~ 815). This is then converted with fluorosulphonic acid methyl ester into 2-phenyl-3-methyl-1,2,3-triazolium fluorosulphonate, which yields, by treatment with N-bromosuccinimide and sodium hydroxide solution, 2 phenyl-3-methyl-1,2,3-~riazolin-4-one (see M. Begtrup et al, Acta Chem. Scand, 25, (1971) 209i). The last-mentioned compound is subsequently converted by reaction with benzoyl chloride into 2-phenyl-4-benzoyloxy-lg2,3-triazole, which yields, with alkaline hydrolysis, 2-phenyl-4-hydroxy-192,3-triazole (see M.
Begtrup,` Acta Chem. Scand. 26, (1972), 715). By an analogous process, it is possible to prepare further compounds of formula III, which are substituted in the phenyl radical , according to the above definition for the radical R3, -starting with corrPspondingly substituted phenylhydrazines.
The compounds thus obtained can be chlorinate~ or brominated in the 4-position. The introductioh of chlorine or bromine in the 4 position ls effected by the action of e.lementary chlorine or bromine in solvents inert to these agents, such as halogenated hydrocarbons. Furthermore, N-chloro-succinimide and N-bromosuccinimide are suitable for the introduction of chlorine and bromine~ respectively With the use o these halogenating agents, ~he procedure is carried out in the aforementioned halogenated hydrocarbons, ~5 particularly in carbon tetrachloride.

The compounds of ~ormula III in which n = O obtained in this manner can . . .
..

' .

5~3 in addition be converted inthe usual manner by the action of hydrogen peroxide or organic peroxy acids, such as peroxy-benzoic acid or m-chloroperoxybenzoic acid, in glacial acetic acid into the corresponding l-oxides.
The starting compounds of the general formula III in which n = 1 and Y = hydrogen can also be advantageously prepar ed by heating an oxime-hydrazone of the formula H0 - ~ = CH - C = N - NH - R (IIIA) . N02 in the presence of a lower aliphatic carboxylic acid at tempera-tures of between 15 and 100C.
The compounds of formula I have a broad biocidal - action, and can be used for the control of various animal and -plant pests.
; ~hey are particularly suitable for the control of insects of the families: Acrididae, Blattidae, Gryllidae, -~-Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudo-coccidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae and Pulicidae;
as well as acarids of the families: Ixodidae, Argasidae, Tetranychidae and Dermanyssidae. Especially advantageous is their use against leaf-eating insects. Some compounds of formula I are also suitable for the control of phytopathogenic nematodes, ; The insecticidal and acaricidal action can be apprec-iably broadened and adapted to suit given circumstances by the addition of other insecticides and/or acaricides. Suitable addi-tives are, for example, organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, pyrethrin-like derivatives, carbamates or chlorinated hydrocarbons.
, - 8 -,. . : . ' : .
,:~ ,, . ., ~, .
.

~ 5 ~
The compounds of formula I can be used on their own or together with suitable carriers and/or additives.
Suitable carriers and additives may be solid or liquid~
and they correspond to the substances common in formulation practice, such as~ for example, natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.
For application, the compounds of formula I can be processed into the form of dus~s, emulsion concentrates, granulates, dispersions, sprays or solutions, the formula~ion of these preparations being effected in a m~nner co.~monly known in practice.
The agents according to the lnvention are prepared in a manner known per se by the inltimate mixing and/or grinding of actlve substances of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances.
The active substances can be obtained and used in the following forms:
1~ solid preparations:- dusts, scattering agents, granulates, -1 coated granulates, impregnated granulates and homogeneous granulates;

_ 9 _ .~ .. . ... .
.
, , '' . ,.,.' ' ' '.. ', , "^ ,',~'. ~ , .~

~ 3 li~uid pree~ations:- .
, a~ water-dispersible ac,tive-substance concentrates:
:~, wettable powders, pastes or emulsions;
b) solutions.

The content of aetive substance in the described ~:, agents is between 0.1 and 95 %. , -' The active substances of formula I can be formulated, for example~ as follows~

,Dusts~
: 10 The following substances are used in the preparation ' of a) a 5% dust, and b) a 2% dust:
a) 5 parts of active substance3 5 parts of talcum;
, b)2 parts of active substance, , : ~
,l 15 1 part of highly dispersed silicic acid, , , ' ' ,~ 97 par~s of talcum. ' '~
', The aetive substances are mi~ed and ground with :~',, the earriers.
. . ; . :.
. .

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

- 10 - ' ' ' , ' - .

.

. . . .
,- , ,' , ., . ~ . . .

' , : ~ ' ' , :

~ S~ ~ 3 Granulate .
The following substances are used to prepare a 5% granulate~
5 parts o active subs~ance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, :~ 9L parts of kaolin (particle size 0.3 ~ 0.8 mm).
The active substance is mixed with epichlorohydrin .
and dissolved with 6 par~s of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin, and : .
the acetone subsequently evaporated off in vacuo~
ettable powder: ~-The ollowing constituents are used for the preparation ~ : :
i 15 o a) a 40%, b) and c) a 25%, and d) a 10~/o wettable po~der:
a~ 40 parts of actlve substance, parts of sodium lignin sulphonate, :l 1 part of sodium dibutyl naphthalene sulphonate, 54 parts of silicic acid; . : :-b) 25 parts of active substance, ~. .
4.5 parts of calcium lignin sulphonate~
1.9 parts o Champagne chalk/hydroxyethyl cellulose ~ -. mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, .l 25 19.5 parts o silicic acid, ~ ~ . - . , 11 --i' /' , , ' ,. . .

~5~ .
l9oS parts of Champagne chalk, 28~1 parts of kaolin, c) 25 parts of active substance,

- 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, -1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin;
d) 10 parts of active substance,

3 parts of a mixture of the sodium salts of ::
saturated atty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde . condensate, i ;lS 82 parts of kaolin.

The active substances are intimately mixed, in suitable mi~ers, with the additives, and the mixture is subsequently ground in the appropriate mills and rollers. Wettable - powders are obtained which can be diluted with water to --, 20 give suspensions of any desired concentration~

Emu] slrl~-ble corcentrates:
The following substances are used to pr~pare a) a 10%
and b) a 25% emulsifiable concentrate:
a) 10 parts of active substance, . 25 3.4 parts of epoxidised vegetable oil, ~,' , ' . ' ;
.

:

3.4 parts of a combination emulsifier consisting o fatty alcohol polyglycol ether and alkylaryl-sulphonate calcium salt, 40 parts of dimethylformamide, S 43.2 parts of xylene;

b) 25 parts of active substance, 2.5 parts of epoxidised vegetab]e oil, parts of an alkylarylsulphonate/fatty alcohol ~ polyglycol ether mixture, - 10 S parts of dime~nylformamide, 57.5 parts of xylene. -From these concen~rates it is possible to prepare, by dilution with water, emulsions of any desired concentration.
, :~ - 1 ' , `
` 1~ ~: :: :.
:j . :~: .
The following constituents are used to prepare a , 5% spray:
; 3 5 parts of active substance, 1 part of epichlorhydrin, ~0 94 parts of ligroin (boiling limits 160 - 190C).

Agent for the ultra low volume sprayin~ technique `.
parts of ac~ive su~stance, parts of epichlorohydrin.
.,,, , , , . ~.

- 13 - - ~ ~
", ' ' ' ' .

" " . . . . .. . . . ..

~ 3 Example 1 A) Preparation of 0,0-diethyl-0-12-p-chlorophenyl-1,2,3-triazox-(2)-yl-(4)]-thiophosphate _ _ _ 12 ml of triethylamine is added dropwise to a colution of 21.1 g of 2-p-chlorophenyl-4-hydroxy-1,2,3-triazole-1-oxide and 19.0 g of diethylthiophosphoric acid chloridein 300 ml of acetonitrile. After 6 hours' refluxing, the reaction mixture is cooled to room temperature, and the formed triethylamine hydrochloride is filtered off. The filtrate is concentrated in vacuo, and subsequently extracted by shaking with ether/water. The ether phase is separated, and dried with sodium sulphate. After removal of the drying agent, the ether is distilled off. The residue is purified through silica gel with 5% of methanol in chloroform as the eluant.
The eluant is distilled off to obtain the compound of the formula S
H ll 0-P(OC2H5)2 0~-N N
~ N /
'.

Cl in the form of oil having a refractlve index. of ~ -728.

'' , '~

.

~ 5~ ~ 3 B) Preparation of 0,0-diethyl-0-[2 phenyl-1,2,3-triazolyl-

(4)]-thiophosphate ':, .
16.1 g of 2-phenyl-4-hydroxy-1,2,3-tria~ole and 18.9 g of diethylthiophosphoric acid chloride are refluxed with 13.8 ml of triethylamine in 300 ml of acetonitrile for

5 hours. The reaction mixture is cooled to room temperature ~nd triethylamine hydrochloride is filtered off. The filtrate is concentrated in vacuo, and subsequently extracted with ether/waterO The ether phase is separated9 and dried with sodium sulphate. After removal of the drying agent, the ether is distilled pff. The residue is purified through silica g~l with chloroform as the eluant.
The eluant is distilled off to obtain the ~ompound of -the formula .. Il .
CH - C-0-P(OC2H5~2 N~ ~N
'~ 1 ~ . ' ., , in the form of yellow oil having a refractive index of n20 = 1.5480.
', :1 .'. .: ' .. .
.. . . .
, , , , '.' .
- 15 - ~
, ., . ' ~, .

,;, . . .
'. ' , " ' ' ~, , I . . . .
, , , "~ , i , , , ,: .
... ,, : , . , ~ , .
. .

~ 5~3 The following compounds are prepared in an analogous manner: X

Y-C ~p< 1 ll ll ~R
(O)I1~-N N 2 ~ 7 .
~ . .
_ _ . , . . ..
R R . X ~n = the ! Physical :~ 1 2 R3 '- , n~ber ¦ data 2 5 -C2H5 ~ S H 1 n2 : 1,563 ~N (CH3) 2 -N (CH3) 2 ~ O . H O n20 : 1,6689 -OCH3 -OCH3 ~ S H 1 n : 1,5765 -SC3H7 (n) -C2H5 ~ S H 1 nD : 1,590 : -SC3H7 tn) -C2H5 ~ S H O nD : 1,5800 . .
., . -~HCH3 -C 2H 5 ~ S H 1 nD : 1,5720 -0~2H5 -C2H5 ~CF3 S H 1. n20: 1,5171 .

OC2~5 -C2H5 -~C1 S H 1 nDO : 1,5753 :
-C2H5 -C2H5 ~ S H 1 - nDO : 1,6625 . - C2~l5 ~C2~l5 -~-C1 S H I . M.P. :56-57 C

C2H5 -C2H5 ~ S C1 O n20 : 1,5552 i; ' _~ _ __ ' _ _ ~ ' '. . . ~ .
, .~ ' ' .

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

~5~5Sii3 .
R R R I Xl Y n = the Physical 1 . 2 3 ~ Inumber data _ __ _ . _ , -C2H5 -C2H5 ~ S Br O nD : 1,5667 ~C3H7~ C2H5 - ~ -Cl S H 1 nD : 1,5894 -Sc3H7( ~) -OC2H5 ~Cl S H 1 nD : 1,6043 -C2H5-C2H5 ~ S H 1 nD: 1,5509 . C~3 . .
_OC2~5-C2H5 - ~ -CH3 S H 1 nD ~ 1,5623 -C2H5-C2H5 ~ S H 1 nD : 1,5542 . . OCH3 .
-C2H5-C2H5 - ~ -OCH3 S ~H 1 n20 : 1,5634 -C2H5C2H5 - ~ -Br S ¦H 1 M~Po: 60-63 C

-C2H5-C2H5 - ~ -F S H 1 nD : 1,5511 -C2H5-C2H5 ~ S H 1 n20 : 1,5709 i, Ccl ' ' ' ~,., ~C2H5. -C2H5 - ~ -F S H 1 n20 : 1,55~8 -OCH3 -OC,H3 ~ S H O
-C2H5 -C2~5. ~ S H 1 .
-C2R5 -OC2H5 ~ S H O
-NHCH3 -C2H5 ~ S H O .
-C2H5 -C2H5 ~ O H 1 :
-C2H5 -OC2~l5 ~ O H O
-Sc3H7(l ) -OC2~l5 ~ O H 1 .
~SC3~l7(n) C2H5 ~ .~ O H O
oc 2~ -C 2H 5 _ ~ _ 5 H O
... _ . :,~;, , ~s~

. _ ~ . . _ Y n - the ! Physical number I data _ . . ...... .. .. _ _ _ I _ ~:~ C2H5 -C2H5 --Cl S H O

¦ - OC 2 H S ~ C 2 H 5 ~-bC2U5 ¦ - C2HS ¦ -~-C 15 ¦H ¦

OC2Hs 1- 2HS ¦ ~3 ' 15 ¦Hr ¦

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

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

~ 5 Exam~le 2 Insecticidal stomach poison action ; ~otton and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion (obtained from a 10%
emulsifiable concentrate).
.
After the drying of the resulting coating, Spodoptera littoralis or Heliothis virescens larvae L3 were placed onto the cotton plants, and Colorada beetle larvae (Leptinotarsa decemlineata) onto ~he potato plants. The test was carried out at 24C with 60% relative humidity.
The compounds according to Example 1 exhibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis, Heliothis virescens and Leptinotarsa decemlineata larvae.
. ~ .
: , .
' ~'' . ~

.. . .

. .

,.
; :
'~
.
.

: .
~, .: . . . :

s~

Example 3 Action a~ainst Chilo suppressalis ; Rice plants of the type Caloro were pl~nted, 6 plants per pot, in plastic pots having a top diameter of 17 cm, and grown to a height of about 60 cm. Infestation with Chilo suppressalis larvae (Ll; 3-4 mm long) was carried out 2 days after application of the active substance in granular form (amount applied - 8 kg of active substance per hectare) to the paddy water. The evaluation of the insecticidal action was made 10 days after application of the granules. . : .
The compounds according to Example 1 were effective against Chilo suppressalis in the above test.

, . . .

~.''.
' ; ' ' ~

~ ' ' ' ~' '.

.-:

~ - 20 -': . . ~ - . - . ~ . .:

~q;35~i53 Example 4 Action a~ainst ticks A) Rhipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube, and subsequently ; 5 immersed for 1 to 2 minutes in 2 ml of an aqueous ~' , emulsion from a dilution series of 100, 10, 1 and 0.1 ppm ~ -,' of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active-substance emulsion could be absorbed by the cotton woo].
, An evaluation in the case of the adults was made after , 2 weeks, and in the case of the larvae after 2 days.
There were two repeats for each test.

` B~ Boophilus microplus (larvae~
. .
~' , 15 With,a dilution series analogous to that in Test A, tests were carried out with 20 sensitive larvae and OP-resistan~ larvae, respectively (resistance is with .
respect to diazinon compatibility).
Compounds according to Example 1 were effective in these tests against adults and larvae of Rhipicephalus bursa and against sensitive and OP-resistant larvae, respectively, of Boophilus microplus.
' ,,: . , "

Example 5 Acaricidal action Phaseolus vulgaris (plants) were infested, 12 hours before the test for acaricidal action, with an infes~ed piece of leaf from a mass culture of Tetranychus urticae.
The transferred mobile stages were sprayed with the emulsified test preparations from a chromatography-sprayer in a manner ensuring no running-off of the spray liquor.
An assessment was made after 2 to 7 days, by examination under a binocular, of the living and of the dead larvae, adults and eggs, and the results were.expressed as percentages.
The treated plants were kept during the "holding time"
ln greenhouse compartments at 25C.
The compounds according to Example 1 were effective in the above test against adults, larvae and eggs of . . . .
Tet~anychas urticae.

. ' . .

' ~ ' .
'' ~ ' - 22 - :

.
- , .

` ~ ~ 5 ~ Example 6 - Actlon a~ainst soil nematodes In order ~o test the action against soil nematodes, the active substances were added, in the concentration stated in each case, to soil infested with root-gall-nematodes (Meloidogyne arenaria); the whole was then intimately mixed. In the one test series, tomato seedlings were planted i~nediately after preparation of the soil .
in this manner, and in the other test series tomatoes were planted after a waiting time of 8 days.
LO For an assessmen~ of the nematocidal action, the galls .
~! present on the roots were counted 28 days after planting and sowing, respectively.
~:~ SomP active substances according to Example 1 exhibited .
in this teRt a good action agains~ Meloidog~ne arenaria.

' .

. . .
'.' - . ~ ~
:.' '~ ' ' , ' :~.
.','', ~:
- 23 ~- ~

" :

, , . . . :
,

Claims

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

1. A compound of the formula wherein R1 represents alkyl, alkoxy, alkylthio, alkoxyalkylthio, amino, mono-alkylamino or dialkylamino, R2 represents alkoxy, alkylthio, amino, monoalkyl-amino or dialkylamino, R3 represents unsubstituted phenyl, or phenyl mono- to trisubstituted, identically or differently, by fluorine, chlorine, bromine and/or iodine, or monosubstituted by methyl, methoxy or trifluoromethyl, Y
represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents oxygen or sulphur.

2. A compound according to claim 1 wherein R1 represents C1-C5-alkyl, C1-C5-alkoxy, C3-C5-alkylthio, methylamino or dimethylamino, R2 represents C1-C5-alkoxy or dimethylamino, R3 represents unsubstituted phenyl, or phenyl mono- to trisubstituted, identically or differently, by fluorine, chlorine, bromine and/or iodine, or monosubstituted by methyl, methoxy or trifluoromethyl, Y represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents oxygen or sulphur.

3. A compound according to Claim 2 wherein R1 represents methyl, ethyl, methoxy, ethoxy, C3-C5-alkylthio, methylamino or dimethylamino, R2 represents methoxy, ethoxy or dimethylamino, R3 represents unsubstituted phenyl, or phenyl mono- to trisubstituted by fluorine, chlorine and/or bromine, or monosubstituted by methyl, methoxy or trifluoromethyl, Y represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents oxygen or sulphur.

4. A compound according to Claim 3 wherein R1 represents methoxy, ethoxy or n-propylthio, R2 represents methoxy or ethoxy, R3 represents unsubstituted phenyl, or phenyl mono- to trisubstituted by fluorine, chlorine and/or bromine, or monosubstituted by methyl, methoxy or trifluoromethyl, Y represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents sulphur.

5. Compound according to Claim 4 of the formula .

6. Compound according to Claim 4 of the formula .

7. Compound according to Claim 4 of the formula .

8. Compound according to Claim 3 of the formula .

9. Compound according to Claim 4 of the formula .

10. Compound according to Claim 4 of the formula .

11. Compound according to Claim 4 of the formula .

12. Compound according to Claim 4 of the formula .

13. Compound according to Claim 4 of the formula .

14. Compound according to Claim 4 of the formula .

15. Compound according to Claim 4 of the formula .

16. Compound according to Claim 4 of the formula .

17. Compound according to Claim 4 of the formula .

18. Compound according to Claim 4 of the formula .

19. Compound according to Claim 4 of the formula .

20. Compound according to Claim 4 of the formula .

21. Compound according to Claim 4 of the formula .

22. Compound according to Claim 4 of the formula .

23. Compound according to Claim 4 of the formula .

24. Compound according to Claim 3 of the formula .

25. Compound according to Claim 4 of the formula .

26. Compound according to claim 3 of the formula

27. Compound according to claim 4 of the formula

28. A process for the preparation of a compound of the formula wherein R1 represents alkyl, alkoxy, alkylthio, alkoxyalkylthio, amino, monoalkylamino or dialkylamino, R2 represents alkoxy, alkylthio, amino, monoalkylamino or dialkylamino, R3 represents unsubstituted phenyl, or phenyl mono- to tri- substituted, identically or differently, by fluorine, chlorine, bromine and/or iodine, or monosubstituted by methyl, methoxy or tri-fluoromethyl, Y represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents oxygen or sulphur, comprising reacting a compound of the formula with a compound of the formula in the presence of an acid binding agent, or with a compound of the formula wherein R1 to R3, X, Y and n have the meanings given above, Hal stands for fluorine, chlorine, bromine or iodine, and Me stands for a monovalent metal.

29. A process according to claim 28 in which Me is an alkali metal selected from sodium and potassium.

30. A method of combatting various animal and plant pests at a locus, which method comprises applying to the locus a compound as claimed in claim 1.

31. A method according to claim 30 for the control of insects and members of the order acarina.

32. A method according to claim 30 for the control of phytopathogenic nematodes.