CA1053233A - Dithiophosphate esters of cyclic pyridine carbamates or thiocarbamates - Google Patents

Abstract

Abstract of the Disclosure Dithi?phosphates of the formula

Description

The present invention relates to dithiophosphates, to processes for their preparation, and to their use in pest control.
The said dithiophosphates correspond to the formula ~ C=X (I) I ~ 11 ~C)R2 P~SR
wherein - 3 Rl represents hydrogen, halogen or nitro, ~2 represents Cl-C5-alkyl, R represen~s Cl-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, Cl-c5-alkoxy-cl-c5-alkyl or cl-~5-alkylthio-Cl C5 alkyl, and X represents oxygen or sulphur.
i~ _ i~ By halogen is meant fluorine, chlorine, bromine and/or ~ iodine. The Cl-C5-alkyl, C3-C5-alkenyl, C3-Cs-alkynyl, 1. .~
Cl-C5-alkoxy-Cl-C5-alkyl and Cl-C~-alkylthio-Cl-C5-alkyl i groups denoted by R2 and R3 can be straight-chain or branched. Examples of such groups are: methyl, methoxy, methoxymethyl, ethyl, ethoxyethyl, ethylthioethyl, propyl, isopropyl, n-butyl, i-, sec.-, tert.-butyl, n pentyl, isopentyl, allyl, methallyl, propargyl and isobutinyl.
Preferred compounds of formula I because of their action are those wherein

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1(~5;3'233 Rl represents hydrogen or chlorine, R2 represents methyl or ethyl, R3 represents n-propyl, iso-propyl, iso-~utyl, methoxyethyl or ethoxyethyl, and X represents oxygen.

The compounds of formula I are prepared by methods known per se, e.g. as follows:

- a) l ~ \C_X + HS- ~ ~ acid-binding ~ I
~/ ~ agent (II) 2 ~l (III) -. . .
b) O
R ~ \ ll ~ if necessary C=X ~ MeS-P< . . . > I
~\N~ N/ ~ acld-bLndlng agent (II) CH2-Cl (IV) i 10 In formulae II, III and IV, the symbols Rl to R3 and X have the meanings given for formula I, and Me stands for a monovalent metal, particularly for an alkali metal such as sodium or potassium. Suitable acid-binding l agents are: tertiary amines, e.g. trialkylamines, pyridine or '~ 15 dialkylanilines; inorganic bases such as hydroxides; carbonates and bicarbonates of alkali metals and alkaline-earth metals.
It is sometimes necessary to use catalysts in the reactions, such as, e.g. copper or copper chloride.

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, ~(J5;~ 3 The reactions a) and b) are perform~d at a temperature of 0-120C, preferably between 10 and 70~C, at normal pressure and in solvents or diluents that are inert to the reactants. The following, for example, are suitable as solvents or diluents: ethers and ethereal compounds, such as diethyl ether, dipropyL ether, dioxane, dimethoxyethane or tetrahydrofuran; amides such as N,N-di-allcylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, especially benzene, toluene, xylenes, chloroform or chlorobenzene;
nitriles such as acetonitrlles; DMS0; ketones such as acetone, methyl ethyl ketone, or mixtures of such solvents with water.

The starting ma~erials of formulae II, III and IV
are known, and can be prepared my methods analogous to known methods.

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~S3Z33 The compounds of formula I have ~ broa~ biocidal action an~ are there~ore suitable for the control of diverse plant and animal pests. They possess however, in particular, insecticidal and acaricidal properties, and can be used against all development stages, such as, e.g. eggs, larvae, pupae, nymphs and adults of insects and members of the order acarina~ such as, e.g.
against insects of the families: Tettigoniidae, Gryllidae, P f ~-h ocor; d oc e Gryllotalpidae, Blattidae, Reduviidae, ~ ~ rrhocorid~c, Cimicidae, Delphacidae, Aphididae, Diaspididae, 5ca~abe ~ da~
Pseudococcidae, ~car~Q~id~c, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae ~ r,`i dae Noctuidae, L~matri~dae-, Pyralidae, Culcidae, Tripulidaes Stomoxydae, Trype~idae, Muscidae, Calliphoridae and ; 15 Pulicidae, as well as acarids of the families: Ixodidae, .. ~rgasidae,- Tetxanychidae and Dermanyssidae.
The insecticidal or acaricidal action can be appreciably broadened and adapted to suit the given circùmstances by the addition of other insecticides and/or acaricides.
Suitable additives are, for example:
organic phosphorus compounds, deriva~ives of nitrophenols, - formamidines, ureas, carbamates, and - chlorinated hydrocarbons.

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1053~33 The active substances of ormula I are suitable also for the control of members of the division thallophyta, such as, e.g. viruses, bacteria and fungi. They thus have fungicidal properties rendering them effective against phytopathogenic fungi in various cultivated crops, such as corn, maize, rice, vegetables, ornamental plants, fruit trees, grape vines, field fruits, etc..
With the new active substances, fungi occurring on fruits, blossom, follage, stalks, tubers and roots can be checked or destro~ed, whereby parts of plants subse~uently growing remain immune against such fungus infestation.
The active substances of formula I are effective especially against phytopathogenic fungi belonging to the following classes: Oomycetes, Zy~omycetes, Ascomycetes, Basidiomycetes and Denteromycetes.
Furthermore, the new active substances are used ~or the treatment of seed~ fruits, tubers, etc. for protection against fungus infections due to, for example, smut fungus of all varieties, such as Ustilaginales, and for the ~ontrol oi phytopathogenic nematodes, .~ . , .

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1(~53Z33 The compounds o~ formula X can bc ~1sed on their own or together with suitable carriers and/or additives.
Suitable carriers and additives may be solid or licluid, and correspond to the substances co~non in ormulation practice, such as, e.g. natural and regenerated substances, solvents, dispersi.ng agents, wetting agents~ adhesives, thickeners, binders and/or fer~ilisers.
For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates) dispersions, sprays~ or solutions, the ~ -formulation of these preparations being effected in a manner commonl)7 known in practice. Also to be mentioned ;~
are cattle dips and spray races, in ~hich aqueous preparations are used.
The agents according to the invention are produced in a manner kno~7n per se by the -intimate mixing and/or grinding o~-active substances of formula I with t11e suitable carri.ers, optionally with the addition of dispersing agents or solvents ~hic11 are inert to the active substances.
The active substances can be obtained and used ~n the i iollowing preparation forms:
~rA~ solid preparations: dusts, scattering agents, granulates~
( coated granulates, impregnated granulates and homogeneous granuiate3;
liquid preparations:
a) water di.spersible active substance concentrates:
wettable powders, pastes, emulsions;
b) solutions.

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105;~Z33 The content of active substance in the described agents is between 0.1 and 95%; it is to be mentioned in this connection that in the case of application from an aeroplane, or by means of other suitable devices, S concentrations of up to 99.5% can be employed, or even the pure active substance.

The active substances of formula I can be prepared, for example, as follows:

~ Dusts:

The ollowing substances are used in the preparation of a) a 5% dust, and b~ a 2% dust:

q a)5 parts of active substance, 95 parts of ~alcum;

b)2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the c-rriers.

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1~53~ 33 Granulate-.
The ~ollo~Jing substances are used to produce a 5% granulate:
5 parts of active substance, 0.25 parts of epichlorhydrin, 0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, - 91 parts o~ kaolin ~ particle si~e 0.3 - 0.8 mm).
The active su~stance is mixed ~ith epichlorhydrin and dissolved with 6 parts of acetone, the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on to kaolin, and the acetone subsequen~ly evaporated off ;n vacuo, Wet~abl~ owder:
... . .
. The following constituents are used or the preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance, ! 5 parts of sodium lignin sulphon~te, 1 part of sodium dibutyl-naph~halene sulphonate, 54 parts of silicic acid.
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20 b) 25 parts of active substance J

4.5 parts o calcium lignin sulphonate 1.9 parts of Champagne challc/hydroxycthyl cellulose mixture (1~
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1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acicl, "~
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5;~ 3 . , 19.5 parts of Champagne cllalk, 28.1 parts o~ kaolin.
c) 25 parts o~ ac~ive sub.s~ance, .5 parts of isooctylpherloY~y-polyoxyethylene-etllanolf 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr9 46 parts o~ kaolin.
d) 10 parts of active substance, 3 parts of a mixture of tlle sodium salts of saturated ~atty alcohol sulphates, S parts of naphthalenesulphonic acid/formaldeh~de condensate, lS 82 parts of kaolin.
The active substances are întimately mixed, in suitable mixers, ~ith the additives, the mixture being then ground in the appropriate mills and rollers; Wett~ble po~ders are obtained which can be diluted ~ith water to give suspensions of any desired concentration.
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Em~11sifiable concentrates:
The following substances are used to produce a) a 10%
and b) a 25% emulsifiable concentrate:
a) lO parts of active substance, 3.4 parts of epoxidised vegetable oil, ,, , , - 10_ .
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~os3~33 7r par~s o~ a combination emulsifier consisting of fatty alcohol polygl~Tcol cther and alkylaryl-sulphonate calcium salt, . 40 parts of dimethyl~ormamide, 43.2 parts of xylene~

b) 25 parts of ac~ive substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alky~arylsulphonate/fatty alcohol-polyglycol e~her mi~ture 5 parts of dimethylformamide, 57.5 parts of xylene.
From these concentrates it is possible to produce, by diluti.on with water, emulsions of any desired concentration.

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The follo~7ing constituents are used to prepare a . 5/O spray ~ 5 parts of active substance, .; 1 part of epichlorhydrin, I 94 parts of ligroin (boiling limits 160-190C).

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1C~53233 Example 1 Pre~ration of 0,S-dimethyl-_-[6-chloro-oxazolo(4,5-b) pyridin-2(3H~-on-3-yl-methyl~-dithiophosphate 22 g of 3-chloromethyl-6-chloro-oxazolo(4,5-b)-pyridin-2(3H~-one, 24 g of potassium salt of 0,S-dimethyl-~ 5 dithiophosphoric acid and 50 ml of methanol are heatedfor 5 minutes at 65C. The methanol is then distilled off . and 100 ml of water added to the residue; the precipitated oil is isolated by extraction with ether to ob~ain the compound CH~jO\ 11 ~ C~
~.P-S-CH2-N 0 10 CH3$/ N

as pale brown, non-distillable oil.
Cal.: C 31.7 H 3.0 N 8.2 P 9.1 S 18.8 Cl 10.4 %
Found: 31.4 3.1 7.8 8.8 18.7 10.7 %

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Also the following compounds were prepared in an analogous manner: :

R ~ \
1 11 C=X ' ~\N ~ N / o il /0~2 ~ 2 ~ SR

.~ Rl R2 ~ X _croanalys,i s .

H CM3 (n)~C3H7- o a) H C2H5 C2H5- O b) H C2 5 (n)-C3H7- O c) . ~ C2~15 (iso)-C3H7~ O d) H C21I5 (n)-C4H9- O e) : .
, 10 ~I C2~15 (iso)-C4~19~ O f) H C2~15 CH30C2~ O g) ~ C2~15 C2H50C2H4- O h) ., . }~ C2}15 CH2=CH CH2- O i) . Cl CH3 (n)-C3H7 O i) : 15 Cl C2M5 C2H5- O k) Cl - C21I5 (n)~C3}I7_ O l) . Gl C2H5 (iso)-C3H7- m~
i Cl C2 5 ~n) C~}19- O n) . Cl C2~15 (iso)-C~H9- O _ _ ,, , . _ .

.. ' ' ~ ' , , ' 5~233 R R R ~ ----- X _______________ 1 2 3 . Microanalysis l __ ~ __ ~
Cl C2HS CH30C2H4- 0M.P, 69-71~G
Cl C~H5 C2H50C2H4- 0'- P) .

¦Cl ¦ C2115 l Ch2 Cll _~ I
:

Microanalysis S a) Cal. C 3~,5 H4,5 N 8,4 P 9,3S 19,2 %
-Fnd. 39,2 4,7 8,0 9,419,5 %

-b) Cal. C 3g,$ H4,5 N 8,4 P 9,3S 19,2 %
Fnd. 39,5 . 4,6 8,3 9,219,0 %

c) Cal- C 41,3 H4,g N 8,0 P 8,9S 18,4 %
10 Fnd. 41,0 5,1 8,0 8,918,2 %
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: d) Cal. C 41,3 H4,9 N 8,0 P 8,9S 18,4 %
Fnd. 41,3 5,1 8,1 8,818,1 %

e) Cal.. C 43,1 H 5,3 N 7,7 P 8,6 S 17,7 %
FndO 42,8 5,3 7,7 8,617,3 %

15 f) Cal. C 43,1 H5,3 N 7,7 P 8,6S 17,7 %
Fnd, 43,0 5,3 7~7 8,717,6 %

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Cal. = Calcula~ed Fnd. = Found .. .. .

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3~33 g) Cal. C 39,6 H 4,7 N 7,7 P 8,5 S 17,6 ~/0 Fnd. 39,5 4,97,5 8,6 17,6 %

h) Cal. C 41,2H S>lN 7,4 P 8,2S 17,0 %
Fnd. 41,1 5,17,3 8,3 16,7 %

5i) Cal. C 41,6 H 4,4 N 8,1 P 9,0S 18,5 %
Fnd. 41,4 4,58,1 9,0 18,4 %

' j) Cal. C 35,8H 3,8 Cl 9,6 N 7,6 P 8,4 S 17,4 %
Fnd. 35,9 4,0 9,8 7,3 8,5 17,4 %
' k) Cal. C 35,8H 3,8Cl 9,6N 7,6P 8,4 S 17,4 %
.Fnd. 36,0 3,8 10,0 7,9 8,1 17,0 %

1) Cal. C 37,6 H 4,2 N 7,3 P 8,1 S 16~7 Cl 9,3 % :
Fnd. 37,6 4,1 7,4 7,8 16,4 9,6 ~/0 m) Cal. C 37,6 H 4,2Cl 9,3 N 7,3P 8,1 S 16,7 %
Fnd. 37,4 4,1 9,S 7,5 7,9 16,5 %
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15n) Cal.C 39,4 H 4,6Cl 8,9N 7,1 P 7,8 S16,2 %
Fnd. 39,1 4,5 9,3 6,8 7,7 16,5 %

o) Cal.C 39,4 H 4,6 Cl 8,9 N 7,1 P 7,8 S 16,2 %
Fnd. 39,1 4,6 9,2 7,2 7,7 16,0 %

p) Cal.C 37,8H 4,4Cl 8,6 N 6,8 P 7,5 S15,5 %
20Fnd. 38,0 4,38,9 6~8 7,4 lS,l %
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,/ q) Cal.C 37,9H 3,7Cl 9,3 N 7,4 P 8,2 S16,8 %
Fnd. 38,1 3,89,6 7,6 8,1 16,5 %

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Example 2 ~Q53Z33 A) Insecticidal stomach poison action Cotton and potato plants were sprayed with a o.o5% aqueous active-substance emulsion (obtained from a 10% emulsifiable concentrate).
After the drying of the obtained coating, Spodoptera littoralis or Heliothis virescens larvae L3 were placed onto the cotton plants~ and Colorada beetle larvae (Leptinotarsa decemlineata) onto the potato plants. The test was carried out at 24C with 60% relative humidity.
The compounds according to Example 1 e~hibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis, ~eliothis and Leptinotarsa decemlineata larvae.
B) SystemQ;c insecticidal action In order to determine the systemic action, rooted bean plants (Vicia faba) were placed into a 0.01% aqueous a~ti~e~substance solution (obtained from a 10% emulsifiable concentrate). After a period of 24 hours~ bean aphids (Aphis fabea) were placed onto the parts of the plants above the soil. The insects were proteated by a special device from the effects of ContaGt and of gas. The test was carried out at 24C with 70% relative humidity.
In the above test, the compounds according to Example 1 exhibited a systemic action against Aphis fabae.

Action a~ainst Chilo suppressalis Rice plants of the type Caloro were planted, 6 plants per pot, in plastic pots having a top diameter of 17 cm, and grown to a height of ca. 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 eval~
uation of the insecticidal action was made 10 days after application of the granules.

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The compounds according to Example 1 were effective against Chilo suppressalis in the above test.
Example 4 Action a~a_nst ticks A) ipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube~ and the test tubes then 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 ~he active substance emulsion could be absorbed by the cotton wool.
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) With a dilution series analogous to that in Test A~ tests were car-ried out with 20 sensitive larvae and OP-resistant larvae, respectively (re-sistance is with respect to diazinon compatibility).
Compounds according to Example 1 were effecti~e in these tests again-st adults and larvae of Rhipicephalus bursa and against sensitive and OP-re-. .
sistant larvae, respectively~ of Boophilus microplus.Example 5 Acarioidal aotion Phaseolus vulgaris (plants) were infested, 12 hours before the test for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae. The transferred mobile stages were sprayed with the emul-sified 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 expressed in percentages. The treated plants were ~l~S3;~33 kept during the l'holding time" in greenhouse compartments at 25 C.
The compounds according to Example 1 were effective in the above test against adults, larvae and eggs of Tetranychus urticae.
Example 6 Action a~ainst soil nematodes In order ~o test the action against soil nematodes the active sub-stances were added~ in the concentration stated in each case, to soil in-fested with root-gall-nematodes (Meloidogyne arenaria), and the whole intim-ately mixed. In the one test series~ tomato seedlings were planted immediat-ely afterwards in the thus prepared soil, and in the other test series to-matoes were planted after a waiting time of 8 days.
Far~an assessment of the nematicidal action~ the galls present on the roots were counted 28 days after planting and sowing, respectively.
Active substances accordlng to Example 1 exhibited in this test a good action against Meloidogyne arenaria.

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Claims (16)

WHAT WE CLAIM IS:

1. Compounds of the formula wherein R1 represents hydrogen, halogen or nitro, R2 represents C1-C5-alkyl, R3 represents C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, C1-C5-alkoxy-C1-C5-alkyl or C1-C5-alkylthio-C1-C5-alkyl, and X represents oxygen or sulphur.

2. Compounds according to Claim 1, wherein R1 represents hydrogen or chlorine, R2 represents methyl or ethyl, R3 represents n-propyl, iso-propyl, iso-butyl, methoxyethyl or ethoxyethyl, and X represents oxygen.

3. Compounds according to Claim 2 of the formula.
.

4. Compound according to Claim 2 of the formula .

5. Compound according to Claim 2 of the formula .

6. Compound according to Claim 2 of the formula .

7. Compound according to Claim 2 of the formula .

8. Compound according to Claim 2 of the formula .

9. Compound according to Claim 2 of the formula .

10. Compound according to Claim 2 of the formula .

11. Compound according to Claim 2 of the formula .

12. Compound according to Claim 2 of the formula

13. Compound according to Claim 2 of the formula

14. Process for the preparation of a compound according to Claim 1, in which process a compound of the formula is reacted 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 and X have the meanings given in Claim 1, and Me stands for a monovalent metal.

15. A method of combating various plant and animal pests at a locus, which method comprises applying to the locus a compound as claimed in Claim 1 on its own or together with suitable carriers and/or additives.

16. A method according to Claim 15 wherein the pests are of the class Insecta or of the order Acarina.