Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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.
- 2 -
-:
., .... . ~ ~ . . ... .. . .. ...... . . . . .. . . . .
., .. . . - , . ;
., . ~,
'' , ' :.
.,... , :
~ a~
JL~7V ~
,~
` 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
~' '
CH3 0 CH3
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
.
. , ,
.
- 3 -
' .
,
. .
. , : . : , : ,. :~
. ,: . . ., : , . .
.
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
-- 4 --
~`' ' .
. .. . . .
.. : -: ' . - . . ~ .
. . .'. , ' ~ ,.,, . ~,
. . . - :
.. - , :
:-
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,
.'` .
- 7 -
' ` ..
..
.. . : . . .: . . . : :: .
-
~ 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,
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 . .
-- 10 --
~ . . . . ~ . : .
. .
[~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
- 13 -
- . . . . - - . .
:- ,. . . . . :,. .
.' '- :' ' ' ' ' ~ ";
,. ~ .
. ' ~ . ,' ' ' '. ~.~:
'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.
- 16 -
,~
.
