CA1080738A

CA1080738A - Pesticidal compositions

Info

Publication number: CA1080738A
Application number: CA280,873A
Authority: CA
Inventors: Jozef Drabek; Manfred Boger
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1976-06-22
Filing date: 1977-06-20
Publication date: 1980-07-01
Also published as: IT1082108B; AU512647B2; TR19827A; ATA436077A; MX4690E; FR2355818B1; AU2628477A; IL52362A; EG12927A; AT353051B; IL52362A0; SU659064A3; GB1579635A; BR7704031A; NL7706779A; FR2355818A1; DE2727614A1

Abstract

Abstract of the Disclosure Compounds of the formula I

Description

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` The present invention relates to novel N,N'-bis-carbamic acid sulphide derivatives which act against pests, to a process for their manufacture and to pesticidal composi-tions which contain these derivatives as active ingredient, and to a method of controlling pests which comprises the use of the novel compounds.
The N,N'-bis-carbamic acid sulphide derivatives according to the invention have the formula I
, c~3~ CH3 / R2 ~C=N--O--C- N ~ S- N (I) ; ' ' . ' wherein Rl represents a methyl or ethyl group, R2 represents a Cl-C~-alkyl or C3-C8-cycloalkyl group and R3 represents a hydrogen ato~ or a Cl-C6-alkoxy or cyclopropyl group.
Alkyl groups R2 can be branched or straight chain.
Possible substituents are for example the methyl, ethyl, n-propyl, isopropyl~ n-butyl, sec.-butyl and tert.-butyl group as well as the n-pentyl, n-hexyl and n-octyl group and the isomers thereof. Such groups, up to and inc7uding hexyl, also form the alkyl moiety of alkoxy groups represented by R3.

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` By C3~C~-cycloalkyl groups are meant cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
Particularly preferred compounds on account of their action against pests, especially against insects, are those of the formula I wherein R2 represent~ a Cl-C4-alkyl, cyclopropyl, cyclohexyl or cyclooctyl group, and represents a hydrogen atom or a Cl-C4-alkoxy or cyclopropyl group.
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- The compounds of the formula I are obtained by methods which are known per se, for example by reacting a compound of the formula II
~' ' C=N--O~-C--N ~ (II) RlS ~ H
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wherein Rl is as defined in formula (I~, in the presence of a base, with a compound of the formula III

Hal- S--N ~ (III) ; Co--R3 .
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wherein R2 and R3 are as defined in formula I and Hal represents a halogen atom, in particular a chlorine or bromine atom.
The process is carried OLlt at a reaction temperature between -20~ and ~80C, at normal or elevated pressure and preferably in a solvent or diluent which is inert to the reactants. Suitable solvents or diluents for the reaction are for example: ethers and ethereal compounds, such as diethyl etherj diisopropyl ether, dioxan, dimethoxyethane and tetrahydrofurane; amides, such as N,N-dialkylated carboxamides;
aliphatic, aromatic and halogenated hydrocarbons, in parti~
cular benzene, toluene, xylenes, methylene chloride, chloro-form and chlorobenzene; nitriles, such as acetonitrile;
dimethyl sulphoxide; and ketones, such as acetone ar~d methyl ethyl ketone.
Suitable bases are tertiary amines, such as tri-ethylamine, dimethyl aniline, pyridine, picolines and luti-dines, and hydroxides, oxides, carbonates and bicarbonates of a~u~i me~s and alka~ne earth m~ as we~ as alkalimetalalcoholates, for example po~assium tert.butylate and sodium methylate.
The compounds of the formulae II and III used as !l starting materials are known (see for example US patent specification 3,506,698) or they can be prepared in accordance with known methods.
The compounds of the formula I have a broad biocidal ~`' ' .
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action and can be used for controlling a variety of pests,for example as insecticides, acaricides, ectoparasiticides, nematicides and fungicides.
The compounds of the formula I are suitable chiefly for controlling insects. They can thus be used for example for controlling insects of the families Lymantrïidae, Noctuidae5 Pyralidae, Tineidae, Bruchidae, Chrysomelidae, Curculionidae, Dermestidae, Scarabaedae, Tenebrionidae, Aphididae, Diaspididae, Cimicidae, Pyrrhocoridae~ Reduviidae, Agromycidae, Anthomyiidae, Calliphoridae, Culicidae, Muscidae, Stomoxidae, Tipulidae, Trypetidae, Acrididae, Blattidae, Gryllidae and Gryllotalpidae.
The compounds of the formula I are suitable in particular for controlling insects which are injurious to plants (e.g insects of the genus Spodoptera, Dysdercus, ~eliothis, Aphis, Pseudococcus and Chilo) in crops of useful plants and in ornamentals, in particular in crops of rice, cotton, fruit and vegetables.
The insecticidal or acaricidal ac~ion can be sub-stantially broadened and adapted to prevailing circumstances by the addition o~ o~her insecticides and/or acaricides.
Examples of suitable additives are: organic phosphorus com-pounds, nitrophenols and derivatives thereof, formamidines, ureas, pyethroids, carbamates, and chlorinated hydrocarbons.
The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or ,, ~, - :: , .: , : , .

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~8~38 ., additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conven~ionally used in the art of formulationg for example natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.
For application, the compounds of the formula I may be processed to dusts, emulsifiable concentrates, granules, dispersions, sprays, to solutions, or suspensions,in the con-ventional formulation which is commonly employed in appli-cation technology.
''' , , The compositions of the present invention are - manufactured in known manner by homogeneously mixing and/or grinding active substanc~s of the ~ormula I with the suitable carriers, with or without the addition of disper-sants or solvents which are inert to the active substances.
The compounds of the formula I may be processed to the following formulations:
Solid formulations:
Dusts, tracking agents and granules ~coated granules, impregnated granules and homogeneous granuLes).
Liquid formulations:
` a) active substances which are dispersable in water:
wettable powders, pastes and em~lsions;
b) solutions.
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The content of active substance in the above des-cribed compositions is generally between 0.1% and 95%
though higher concentrations can also be used if the compositions are applied from an aircraft or other appropriate application devices~
The compounds~active substances~ of the formula I
can, for example, be formulated as follows (throughout the present specification all pa~ts and percentages are by weight~:
usts.
The following substances are used to manufacture a) a 5% and b) a 2% dust:
a) 5 parts of active substance, 9S parts of talc;
b) 2 parts of active substance, 1 part of highly disperse silicic acid, 97 parts of talc.

The active substances are mixed with the carriers and ground.
Granules The following substances are used to produce 5%
granules:
; 5 parts of active substance~
0.25 parts of epichlorohydrin, .'` .

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0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0 3 - 0.8 mm).
The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The re-sultant solution is sprayed on kaolin, and the acetone is subsequently evaporated in vacuo.

Wettable powder: .
The following eonstituents are used for the pre-~i paration of a) a 40%, b) and c) a 25%, and d) a 10% wettable powdex:
a)~0 parts of active substanceg 5 parts of sodium lignin sulphonate, 1 part of sodium dibutylnaphthalenesulphonate, 54 parts of silicic acid.
b)25 par~s of active subs~ance,

4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulosemixture (1~
1.5 parts of sodium dibutylnaphthalenesulphonate, 19~5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 par~s of kaolin, .. . . . . . . .
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c)25 parts of active substance, 2,5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts o~ Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8,3 parts of sodium aluminium silicate, 1605 parts of kieselguhr, 46 parts of kaolin;
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~ d)10 parts of active substance, -~ 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, :.
82 parts o kaolin.
The active substances are homogeneously mixed with - ~he additives in suitable mixers ~nd the mixture is then ground in appropriate mills and rollers. Wettable powders . .......................................................................... .
are obtained which can be diluted with water to give sus-pen~ions of the desired concentration.
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Emulsifiable concentrates . ;` ,.
The following substances are used to produce a) a 10%, b) a 25%, and c) a 50% emulsifiable concentrate:
a~ 10 parts of active substance7 ~ -3.4 parts of epoxidised vegetable Oilg ' ' :
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3.4 parts o a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, parts of dimethyl formamide, 43.2 parts of xylene;
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, ~l 10 parts of alkylarylsulphonate/fatty alcohol : polyglycol ether mixture, parts of dimethyl formamide, 57~5 parts of xylene;
c) 50 parts of active substance, . ~
- 4.2 parts of tributylphenol-polyglycol ether,

5.8 parts of calcium dodecylbenzenesulphonate, parts of cyclohexanone, parts of xylene.
`. By diluting these concentrates with water it is possible to obtain emulsions of the required concentration.

Spray~
The following ingredients are used to prepare a) a 5% spray, and b~ a 95% spray:
~ a) 5 parts of active substance, 1 part of epichlorohydrin, ~: 94 parts of ligroin (boiling range 160-190C~;

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` b) 95 parts of active substance, S parts of epichlorohydrin.
.. The invention is further illustrated by the following Examples.

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3 0 6 13( ) .

(Compound 1) with a melting point of 45C.
The ollowing compounds of the formula I can be obtained in analogous manner:

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CH3 ,0, CH3 / 2 C = ~0--~N--S--N
RlS/ COR3 ~,~,.. ~_. _ . _ .. .. _. . _ _ _ Compound Rl R2 R3 PhysLcal . __ _ _ _ _ ~
2 3 CH3- _ m. p, 55- S 9 C

3CH3 - CH3 - 3 nD: 1 . 5 307 .. . .. _. _ . . ~ _ . . .
_ CU3- ~_ H n2 1. 552 9 5OEl3- ~n) C4Hg- ) 4 9 m.-p. 62 - 66 C

. C2H5- CH3- n~C6H130 n22: 1. 5100 7 CH3- CH3- H ~20: 1~ 5450 . ~ __ 8C2H5-_ CH3- H . n20: 1. 5407 :

g CH3- (n)C4Hg 3 . mOl?. 90C
. . _. . . . _ .~ . .___ 10C2H5- ~n)C4Hg ~H30 n~: 1 . 5099 _ _ _ ~ _ .
11C2H5- ~ CH ~- 1~ -~-9p. 104-106C
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12CH3-- cyclooctyl H n20: 1. 5534 .. , _. . _ 13 C2HS- cyclooctyl H n20: 1. 5483 _ CH3- ~ _ m . p. 54 58C

C2H5- H nD: lo 5468 - . . . . - - . .
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17 C2H5 CH3 (n)C4Hg- n20: 1~5158 ~__ _ . . 20 ; 18 CH3 ( )C H ~ 2 H nD : 1~5218 . C2H _ ¦ ¦ C~H5 ¦ \ CH-CH2.¦ H ¦ n20 :
' ' ' Example 2 Insecticidal stomach poison act-ion: Spodoptera littoralis, Dysdeec~s ~-ci-tu~ and Heliot ;s virescens Cotton plants were sprayed with an aqueous emulsion : containing 0.05% of the compound to be tested (obtained from a 10% emulsifiable concentrate~
After the spray coating had dried, the plants were populated with larvae (L3-stage) of the species Spodoptera littoralis, Dydercus ~asciatus or ~eliothis virescensO Two plants were used or each test ~ompound and test species.
Evaluation of mortality was made after 2, 4, 24 and 48 hours.
-; The test was carried out at 24C and 60% relative humidity ~ 14 -:~' , ~ :
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In this test, the compounds of Example 1 exhibited a very gosd action against larvae of the species Spodoptera lottoralis, Dysdercus fasciatus and Heliothis virescens.

Insecei~-d-l con t action: Aphis fabae Plan~s (Vicia faba) which have been reared in pots were each populated before the start of the test with approx.
200 aphids of the species Aphis fabaeD The treated plants were sprayed dripping wet 24 hours later with a solution i containing 1000 or 100 ppm of the compound to be tested.
Two plants were used for each test compound and test concen-tration. Evaluation of mortality was made 24 hours later.
In this test, the compounds vf Example 1 exhibited - a positive action against Aphis fabaeO

Example 4 Plants (Vicia faba) which have been reared in pots and cut back to a well-developed pair of lea~es, were populated with approx. 200 lice of the species Pseudococcus citri 24 hours before the start of the test. The undersides of the leaves populated with lice were then sprayed dripping wet next day with a test solution containing 500 ppm of the compound to be tested. Two plants were used for each test . .
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In this test, the compounds of Example 1 acted against Pseudococcus citri.
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Example 5 Insecticid_l_action. Chilo_suppressalis Rice seedlings of the variety Caloro were reared in plastic pots (6 seedlings per pot) so that their roots became matted to a disc. The roots were then immersed in a solution - con~aining 800, 200 or 100 ppm of the active compound ~o be tested and allowed to drip off. Then each pot was populated with 5 Chilo suppressalis larvae in the L2-stage and the treated plants were subsequently replaced in the po~s on top of the larvae.
One plant was used for each test substance and concentration, and evaluation of mortality (in %) was made after 5 days. The test was carried out at 24C and 70% relative humidity.
In this test, the compounds of Example 1 exhibited a good action against Chilo suppressalis.

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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 I

(I) wherein R1 represents a methyl or ethyl group, R2 represents a C1-C8-alkyl or C3-C8-cycloalkyl group and R3 represents a hydrogen atom or a C1-C6-alkoxy or cyclopropyl group.

2. A compound as claimed in claim 1 wherein R2 represents a C1-C4-alkyl, cyclopropyl, cyclohexyl or cyclooctyl group and R3 represents a hydrogen atom or a C1-C4-alkoxy or cyclopropyl group.

3. The compound according to claim 1 of the formula .

4. The compound according to claim 2 of the formula .

5. The compound according to claim 2 of the formula .

6. The compound according to claim 2 of the formula .

7. The compound according to claim 2 of the formula .

8. The compound according to claim 1 of the formula .

9. The compound according to claim 2 of the formula .

10. The compound according to claim 2 of the formula .

11. The compound according to claim 2 of the formula .

12. The compound according to claim 2 of the formula .

13. The compound according to claim 2 of the formula .

14. The compound according to claim 2 of the formula .

15. The compound according to claim 2 of the formula .

16. The compound according to claim 2 of the formula .

17. The compound according to claim 2 of the formula .

18. The compound accordîng to claim 2 of the formula .

19. The compound according to claim 2 of the formula .

20. The compound according to claim 1 of the formula .

21. The compound according to claim 1 of the formula .

22. A method of controlling pests at a locus which method comprises applying to said locus a compound as claimed in any one of claims 1 to 3.

23. A method of controlling insect pests at a locus which method comprises applying to said locus a compound as claimed in any one of claims 1 to 3.

24. A method of controlling insect pests in agricultural or horticultural crops which method comprises applying to said crop a compound as claimed in any one of claims 1 to 3.

25. A method of controlling insect pests in vegetable or fruit crops which method comprises applying to said crop a compound as claimed in any one of claims 1 to 3.