CA1080738A - Pesticidal compositions - Google Patents
Pesticidal compositionsInfo
- Publication number
- CA1080738A CA1080738A CA280,873A CA280873A CA1080738A CA 1080738 A CA1080738 A CA 1080738A CA 280873 A CA280873 A CA 280873A CA 1080738 A CA1080738 A CA 1080738A
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure Compounds of the formula I
Description
i7~f~
. .
` 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.
. .
` 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.
- 2 --:
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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.
. .
- 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
.
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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` 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.
. .
- 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
.
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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.
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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 ~`' ' .
. .. . . .
.. : -: ' . - . . ~ .
. . .'. , ' ~ ,.,, . ~, . . . - :
.. - , :
:-73 ~
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 ,, ~, - :: , .: , : , .
:
. , ~ .
~ .. .. : - , : .. ~
.
~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.
.'1 ' '''" .
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. . . .
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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, .'` .
' ` ..
..
.. . : . . .: . . . : :: .
-~ 73~
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,
, . .
. , : . : , : ,. :~
. ,: . . ., : , . .
.
7~
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 ~`' ' .
. .. . . .
.. : -: ' . - . . ~ .
. . .'. , ' ~ ,.,, . ~, . . . - :
.. - , :
:-73 ~
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 ,, ~, - :: , .: , : , .
:
. , ~ .
~ .. .. : - , : .. ~
.
~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.
.'1 ' '''" .
~ 6 -, .. . .. . . ...... . . . . .
. . . .
:. ~ . .~, . . . . ..
,. , . . : . . .: ~ :
.' ' . -.
73 ~
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, .'` .
' ` ..
..
.. . : . . .: . . . : :: .
-~ 73~
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, .. . . . . . . .
.
.
.. . ~ . .
.
.
.
,: . . , , ~ .
73~
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;
~ . .
~ 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.
.; ~.
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 ' ' :
_ 9 _ . .
3~
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,
1.5 parts of sodium dibutylnaphthalenesulphonate, 19~5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 par~s of kaolin, .. . . . . . . .
.
.
.. . ~ . .
.
.
.
,: . . , , ~ .
73~
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;
~ . .
~ 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.
.; ~.
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 ' ' :
_ 9 _ . .
3~
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~;
,v . .
~ . . . . ~ . : .
. .
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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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i ' . ! , ' . . ' , , . , ' ' ' ~'~' .' . ' ' ' " ' ' . : ' . '' ' ' . ' ' ' ' ' , ', " ' . .' " " , ~, " ' , ', ~' '' ' ' ' ' ' .' ,, ' ,' . ',. ., ~ ' ' ' ', 8~t73 Example 1 -Preparation of N-(N-methylcarbamic acid-l-methylthioethyl-imide)~N'-(N'-methylcarbamic acid-n~hexyl ester)-sulphide With stirring~ 15.8 g of N-chlorosulphenyl-N-methyl-n-hexylurethane and then 6.6 g of pyridine were added dropwise at 5 to 10C to a solution of 11.3 g of l-methyl-thioethylidenamino-N-methylcarbamate in 70 ml of dichloro-methane. The reaction mixture was then stirred for 16 hours at a temperature of 5 to 10C~ The pyridine hydrochloride which had formed was subsequ~ntly filtered off by suction, the dichloromethane distilled off, and the crude product chromatographed over silica gel (benzene/methyl acetate3, giving the N-(N-methylcarbamic acid-l-methylthioethylimide)-N'-~N'-methylcarbamic acid-n-hexyl ester~-sulphide of the formula CH3,~ ~H3 / CH3 C=N----O----C~ N--~ -N
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:
., s 3~
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
_ _.
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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. Compound Rl R2 ~3 Physical ;. .... __ ... ... . .. . ~ .
. 16 CH3 CH3 ( ) 4 9 ~.p.45-47C
,. . ____ . , . ... _ . _ _ . .
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 -:~' , ~ :
.
. ' , ~ 7 3~
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 . .
; - 15 -~ .
.. . . . . . . . . . ..
- . . .. - , .- .. : . . . . .
.: . . ,. . : ~ . : .
. ~ ' ' ,' ' ' ' .' . . ' ' .
lOB~738 substance and evaluation of mortality was made 24 and 48 hours respectively after the start of the test.
In this test, the compounds of Example 1 acted against Pseudococcus citri.
.
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.
,~
.
`. 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~;
,v . .
~ . . . . ~ . : .
. .
[~t73~
., .
` b) 95 parts of active substance, S parts of epichlorohydrin.
.. The invention is further illustrated by the following Examples.
~, .
.'~ ' ' .
.
.' ' ' .
, ' :
i . ~ .
, . . ,i : :.
.~~ ' .:
:
.. . .
1 ` . ::
, .
:,, !
:.`- .
,' -.~, .
i ' . ! , ' . . ' , , . , ' ' ' ~'~' .' . ' ' ' " ' ' . : ' . '' ' ' . ' ' ' ' ' , ', " ' . .' " " , ~, " ' , ', ~' '' ' ' ' ' ' .' ,, ' ,' . ',. ., ~ ' ' ' ', 8~t73 Example 1 -Preparation of N-(N-methylcarbamic acid-l-methylthioethyl-imide)~N'-(N'-methylcarbamic acid-n~hexyl ester)-sulphide With stirring~ 15.8 g of N-chlorosulphenyl-N-methyl-n-hexylurethane and then 6.6 g of pyridine were added dropwise at 5 to 10C to a solution of 11.3 g of l-methyl-thioethylidenamino-N-methylcarbamate in 70 ml of dichloro-methane. The reaction mixture was then stirred for 16 hours at a temperature of 5 to 10C~ The pyridine hydrochloride which had formed was subsequ~ntly filtered off by suction, the dichloromethane distilled off, and the crude product chromatographed over silica gel (benzene/methyl acetate3, giving the N-(N-methylcarbamic acid-l-methylthioethylimide)-N'-~N'-methylcarbamic acid-n-hexyl ester~-sulphide of the formula CH3,~ ~H3 / CH3 C=N----O----C~ N--~ -N
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:
., s 3~
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
_ _.
12CH3-- cyclooctyl H n20: 1. 5534 .. , _. . _ 13 C2HS- cyclooctyl H n20: 1. 5483 _ CH3- ~ _ m . p. 54 58C
C2H5- H nD: lo 5468 - . . . . - - . .
:- ,. . . . . :,. .
.' '- :' ' ' ' ' ~ ";
,. ~ .
. ' ~ . ,' ' ' '. ~.~:
'7~
., .
~ _ .. .. . ~v~
. Compound Rl R2 ~3 Physical ;. .... __ ... ... . .. . ~ .
. 16 CH3 CH3 ( ) 4 9 ~.p.45-47C
,. . ____ . , . ... _ . _ _ . .
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 -:~' , ~ :
.
. ' , ~ 7 3~
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 . .
; - 15 -~ .
.. . . . . . . . . . ..
- . . .. - , .- .. : . . . . .
.: . . ,. . : ~ . : .
. ~ ' ' ,' ' ' ' .' . . ' ' .
lOB~738 substance and evaluation of mortality was made 24 and 48 hours respectively after the start of the test.
In this test, the compounds of Example 1 acted against Pseudococcus citri.
.
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.
,~
.
Claims (25)
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.
(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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH767936A CH608692A5 (en) | 1976-06-22 | 1976-06-22 | Pesticide comprising an N,N'-dicarbamic acid sulphide derivative as active ingredient |
| CH601577 | 1977-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1080738A true CA1080738A (en) | 1980-07-01 |
Family
ID=25698832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA280,873A Expired CA1080738A (en) | 1976-06-22 | 1977-06-20 | Pesticidal compositions |
Country Status (14)
| Country | Link |
|---|---|
| AT (1) | AT353051B (en) |
| AU (1) | AU512647B2 (en) |
| BR (1) | BR7704031A (en) |
| CA (1) | CA1080738A (en) |
| DE (1) | DE2727614A1 (en) |
| EG (1) | EG12927A (en) |
| FR (1) | FR2355818A1 (en) |
| GB (1) | GB1579635A (en) |
| IL (1) | IL52362A (en) |
| IT (1) | IT1082108B (en) |
| MX (1) | MX4690E (en) |
| NL (1) | NL7706779A (en) |
| SU (1) | SU659064A3 (en) |
| TR (1) | TR19827A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4497746A (en) * | 1980-10-02 | 1985-02-05 | Ciba-Geigy Corporation | Benzamidosulfenylcarbamoyl halides |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2737606A1 (en) * | 1977-08-20 | 1979-03-01 | Bayer Ag | ARYL-N-ALKYL-CARBAMATE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES |
| DE2828133A1 (en) * | 1978-06-27 | 1980-01-10 | Bayer Ag | N-SULFENYLATED CARBAMOYLOXIMINO-1-METHYLTHIO-BUTANES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES |
| JPS5892655A (en) * | 1981-11-27 | 1983-06-02 | Otsuka Chem Co Ltd | Carbamate derivative, its preparation and insecticide containing said derivative as active component |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2530439C2 (en) * | 1974-07-11 | 1983-03-03 | CIBA-GEIGY AG, 4002 Basel | Bis- [0- (1-alkylthio-ethylimino) -N-methyl-carbamic acid] -N, N'-sulfides, processes for their preparation and pesticides containing these compounds |
-
1977
- 1977-05-21 IT IT24907/77A patent/IT1082108B/en active
- 1977-06-20 TR TR19827A patent/TR19827A/en unknown
- 1977-06-20 FR FR7718846A patent/FR2355818A1/en active Granted
- 1977-06-20 CA CA280,873A patent/CA1080738A/en not_active Expired
- 1977-06-20 DE DE19772727614 patent/DE2727614A1/en not_active Ceased
- 1977-06-20 NL NL7706779A patent/NL7706779A/en not_active Application Discontinuation
- 1977-06-21 EG EG365/77A patent/EG12927A/en active
- 1977-06-21 MX MX775830U patent/MX4690E/en unknown
- 1977-06-21 AU AU26284/77A patent/AU512647B2/en not_active Expired
- 1977-06-21 BR BR7704031A patent/BR7704031A/en unknown
- 1977-06-21 AT AT436077A patent/AT353051B/en not_active IP Right Cessation
- 1977-06-21 GB GB25871/77A patent/GB1579635A/en not_active Expired
- 1977-06-21 IL IL52362A patent/IL52362A/en unknown
- 1977-06-22 SU SU772498355A patent/SU659064A3/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4497746A (en) * | 1980-10-02 | 1985-02-05 | Ciba-Geigy Corporation | Benzamidosulfenylcarbamoyl halides |
Also Published As
| Publication number | Publication date |
|---|---|
| IL52362A0 (en) | 1977-08-31 |
| GB1579635A (en) | 1980-11-19 |
| MX4690E (en) | 1982-08-02 |
| FR2355818A1 (en) | 1978-01-20 |
| ATA436077A (en) | 1979-03-15 |
| EG12927A (en) | 1980-10-31 |
| IT1082108B (en) | 1985-05-21 |
| DE2727614A1 (en) | 1978-01-05 |
| FR2355818B1 (en) | 1980-03-14 |
| AU2628477A (en) | 1979-01-04 |
| BR7704031A (en) | 1978-06-06 |
| AT353051B (en) | 1979-10-25 |
| SU659064A3 (en) | 1979-04-25 |
| NL7706779A (en) | 1977-12-27 |
| TR19827A (en) | 1980-01-24 |
| AU512647B2 (en) | 1980-10-23 |
| IL52362A (en) | 1980-12-31 |
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