Note: Descriptions are shown in the official language in which they were submitted.
5'~
- The present invention relates to novel thiosubstituted
carbamic acid derivatives which act against pests, to a process
for their manufacture and to pesticidcll comllositiorls which contai~
these derivatives as active ingredient, to a method of controlling
pests which comprises the use of the novel compounds, and to a
process for preparing such novel compounds.
The thiosubstituted carbamic acid derivatives of the
present invention have the formula
Rl R3 CH3 0 R
~ , " / 4
P - N S N - C - - 0 N=C (I)
R / SR5
wherein
Rl and R2, each independently of the other, is methoxy, ethoxy,
or dimethylamino,
R3 is methyl, ethyl, n-butyl, cyclopropyl or cyclopropylmethyl,
R4 is methyl or ethyl and
R5 i5 cl-C5~alkYl~ -
with the proviso that when Rl and R2 each is ethoxy, R3, R4 and
R5 are not methyl at the same time.
Alkyl groups represented by R5 can be branched or straight-
chain. Such groups can be for example the methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec- and tert-butyl group, as well
as the n-pentyl group and the isomers thereof.
In the compounds of the formula I, the following sub-
stituents and combinations thereof are preferred:
i) for Rl and R2: methoxy and ethoxy;
~ .
- I
" 1~75'~
ii) for R3: methyl, ethyl, n-butyl, cyclopropyl, and cyclopropyl-
methyl, in particular methyl and cyclopropyl;
iii) for R4: methyl; and
iv) for R5: methyl and ethyl.
The following compound subgroups are particularly prefer-
red:
i) compounds of the formula I wherein Rl, R2, R3, R4 and R5
have the following value in combination:
(1) Rl= methoxy, R2 = methoxy, R3 = methyl, R4 = methyl and
R5 = m~thyl,
(2) Rl =methoxy, R2 = methoxy, R3 = methyl, R4 = methyl and
R5 = ethyl,
(3) Rl =ethoxy, R2 = ethoxy, R3 = methyl, R4 = methyl and
R5 = ethyl,
(4) Rl =ethoxy, R2 = ethoxy, R3 = cyclopropyl, R4 = methyl and
R5 = methyl,
(5) Rl = dimethylamino, R2 = dimethylamino, R3 = methyl,
R4 = methyl and R5 = methyl,
(6) Rl = methoxy, R2 = methoxy, R3 = methyl, R4 = ethyl and
R5 = methyl,
(7) Rl = methoxy, R2 = methoxy, R3 = ethyl, R4 = methyl and
R5 = methyl,
(8) Rl = methoxy, R2 = methoxy, R3 = n-butyl, R4 = methyl and
R5 = methyl,
(9) Rl = methoxy, R2 = methoxy, R3 = n-butyl, R4 = methyl and
R5 = ethyl,
~~ 3 -
(10) Rl = methoxy, R2 = methoxy, R3 = cyclopropylmethyl,
R4 = methyl, R5 = methyl,
(11) Rl = ethoxy, R2 = ethoxy, R3 = methyl, R4 = methyl, and
R5 = n-amyl, ~
(12) Rl = methoxy, R2 = dimethylamino, R3 = methyl, R4 = methyl
and R5 = methyl.
Compounds of the formula I wherein Rl, R2, R3, R4 and R5
have the following value in combination:
(1) Rl = methoxy, R2 = methoxy, R3 = methyl, R4 = methyl and
R5 = methyl,
(2) Rl = methoxy, R2 = methoxy, R3 = methyl, R4 = methyl and
R5 = ethyl,
(3) Rl = ethoxy, R2 = ethoxy, R3 = methyl, R4 = methyl and
R5 = ethyl,
(4) Rl = ethoxy, R2 = ethoxy, R3 = cyclopropyl, R4 = methyl and
R5 = methyl.
The present invention also provides a process for pre-
paring the compounds of the formula I which process comprises
reacting a compound of formula II
Rl 11 IR3
/ P - N - S - X (II)
R2
- 3a -
~ 5 ~
in which Rl and R2 are as defined in formula I and X is a
halogen atom, i.n particular a chlorine or bromine atom, in
the presence of a base with a compound of the formula III
H / 4
j N - C - 0 - N ~ C (~II)
C~13 SR5
in which ~4 and ~5 are as defined in formula I.
The process is sui~bly carried out at a reaction. temperature
between -20 and ~80C, usually between -10 and ~40C, at
normal or elevated pressure and preferably in a solvent or
diluent which. is inert to the reactants. Suitabl.e solvents
or diluents for the reaction are for example: ethers and
ethereal compounds, such as dipropyl e~her, dioxan, dimethoxy-
ethane and tetrahydrofurane; amides, such as N,N-dialkylated
carboxamides; aliphatic, aromatic and halogenated hydrocarbons,
in particular benzene, toluene, xylenes, methylene chloride,
chloroform and chlorobenzenei nitriles, such as acetonitrile;
dimethyl sulphoxidei and ketones, such as acetone and methyl
ethyl ketone.
Suitable bases for the above reaction are tertiary
amines, such as triethylamine, dimethyl aniline, pyridine,
picolines and lutidines, and hydroxides, oxides, carbonates
and bicarbonates of alkali metals and alkaline earth metals
as well as alk~li metal alcoholates, for example potassium
~:~75~1
tert. butylate and sodium methylate.
The starting materials of the formulaIII are known (cf.
R. WEGLER: "Chemie der Pflanzenschutz- und Schadlings-
bekampfungsmittel", Springer Verlag 1970, pp. 219-245) or they
can be prepared in accordance with known methods.
The starting materials of the formula II are new. They
can also be prepared by known methods, for example by reacting
a compound of the formula IV
Rl \ / R3 (IV)
R \ H
wherein Rl, R2 and R3 are as defined in formula I, in the presence
of a base, with sulphur dichloride (SC12).
Accordingly the present invention further provides a
process for preparing the compound as defined in formula I, which
process comprises (1) reacting a compound of formula IV
1 0 R3
\11 /
p - N \ (IV)
2 H
wherein Rl, R2 and R3 are as defined in formula I, with sulphur
dichloride in the presence of a base, thereby preparing a compound
of formula II
R 0 R
1 \ 11 13
/ P - N ~ S X (II)
R2
~ . }
~ i~. _ 5
~ ~'7~
wherein Rl, R2 are as defined in formula I, and X is a halogen
atom, and (2) reacting the compound of formula II with a compound
of formula III
H 0 / R4
N - C 0 - N=C (III)
CH3 R5
wherein R4 and R5 are as defined in formula I, in the presence
of a base.
The compcunds of the formula I have a broad biocidal
action and can be used for controlling a variety of pests, for
example as acaricides, insecticides or ectoparasiticides.
Accordingly the present invention still further provides
a method of controlling insect pests at a locus which method
comprises applying to said locus a compound as defined in formula
I.
The compounds of the formula I are suitable in particular
for controlling insects, chiefly for controlling insects which
are harmful to plants and animals, for example insects of the
families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae,
Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae,
Delphacidae, Pseudococcidae, Chrysomelidae, Coccinellidae,
Bruchidae, Scarabaeidae, Dermestididae, Tenebrionidae, Curculionidae,
Tineidae,
- 5a -
~ ~7 ~
Noctuidae, Lymantriidae, Pyralidae, Galleril~ae,Culicidae,
Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trype~idae
and Pucilidae.
The compounds of the formula I can thus be usecl
according to the invention for controlling insects which .
damage plants in crops of cotton, vegetable and fruit. In
this connection, particular mention is to be made of the
fact that individual compounds of the formula I have both a
systemic and a stomach poison and contact action against
sucking insects, for example aphids.
The insecticidal or acaricidal action can be sub-
stantially broadened and adapted to prevailing circumstances
by the addition of other insec.icides and/or acaricides.
Examples of suitable additives are: organic phosphorus co~-
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
additives. Sultable carriers and additives can be solid or
liquid and correspond to the substances conventionally used
in the art of formulation, for example natural or regenerated
substances, solvents, dispersants, wetting agcnts, tacklfiers,
thickeners, binders and/or fertilisers.
For appli.cation, the compounds of thc formula I may
bc processed to dusts, emulsifiable conccntrates, gL-an.les,
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 substances of the formula I with the suitable
carriers, with or without the addition of dispersants 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 powders and granules (coated granules,
impregnated granules and homogeneous granules).
Liquid formulations:
a) active substances which are dispersable in water:
wettable powders, pàstes and emulsions
b) solutions.
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 :~
can, for example, be formulated as follows (throughout .he
present specification all parts and percentages are ~y
weight):
- 7
~ ~ ~5
Dusts
The following substances are used to manufacture
a) a 5% and b) a 2% dust:
a) 5 parts of active substance,
95 parts of talci
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:
parts of active substance,
0.25 parts of epichlorohydrin,
0.25 parts of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (particle size 0.3 - 0.8 m~).
The active substance is mixed with epichlorohydrin
and dissolved with 6 parts of acetonei 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 constituents are used for the pre-
paration of a) a 40%, b) and c) a 25%, and d) a 10% wettable
powder:
a) 40 parts of active substance,
S parts of sodium lignin sulphonate,
1 part of sodium dibutylnaphthalenesuiphonate,
54 parts of silicic acid.
b) 25 parts of active substance,
4.5 parts of calcium lignin sulphonate,
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mixture (1:1),
1.5 parts of sodium dibutylnaphthalenesulphonate,
19.5 parts of silicic acid,
19.5 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 fatty alcohol sulphates,
parts of naphthalenesulphonic acid/formalde.l~-de
_ 9 _
11 75
condensate,
82 parts of kaolin.
The active substances are homogeneously mixed with
the additives ln suitable mixers and the mixture is then
ground in appropriate mills and rollers. Wettable powders
are obtained which can be diluted with water to give sus-
pensions 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 substance,
3.4 parts of epoxidised vegetable oil,
3.4 parts of a combination emulsifier consisting of
fatty alcohol polyglycol ether and
alkylarylsulphonate calcium salt,
par~s of dimethyl formamide,
43.2 parts of xylene;
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
parts of alkylarylsulphonate/fatty alcohol
polyglycol ether mixture,
parts of dimethyl formamide,
57.5 parts of xylene;
c) 50 parts of active subs~ance,
4.2 parts of tributylphenol-polyglycol ether,
- 10 -
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.
~ .
The following ingredients are used to prepare a~ a
5% spray, and b) a 95% spray:
a) S parts of active substance,
1 part of epichlorohydrin,
94 parts of ligroin (boiling range 160-190C);
b) 95 parts of active substance,
parts of epichlorohydrin.
The invention is further illustrated by the following
Egamples.
~L~Ltj~
Example 1
Preparation of 3,7-dimethyl-5-oxa-4,7,9-triaza-2,8-dithia-6-
oxa-9-dimethylphosphoryl-decene(3)
_
To a solution of 15.3 g of S-methyl-N-(methyl-carbamoyl)-oxy-
thioacetamidate in 100 ml of methylene chloride were added
dropwise at a temperature of 0C 19.5 g of dimethyipllosphoryl-
N-methylamide-sulphonyl chloride and subsequently 12 g of
pyridine. The reaction mixture was stirred for a further 12
hours a~ 0 to 5C. The reaction solution was filtered by suct-
ion and the methylene chloride distilled off. The crude
product was dissolved in benzene, and the benzene solution was
filtered by suction and the benzene distilled off. The product
was chromatographed (silica gel 60/methyl acetate), affording
the compound of the formula
CH 0 0 CH CH 0 CH
3 ~ i~ 1 3 1 3 n ~ 3
~ P - N ~ S - N - C - 0 - N - C ~
CH30 SC~3
(compound 1) with a rnelting point of 52-56C.
The following compounds of the formula I
- 12 -
3L1~54~
Rl \ R3 CH3 ,0, R4
P - N - S - N - C - 0 - N = C: (I)
R2 ~ \`SR
are obtained, or can be obtained, in analogous manne~:
~ ¦!
Compound Rl R2 R3 R4 R5 Physical data
2 CH30 CH30 CH3 CH3 C2H5 nD :1.5190
I _...................... ,_
3 C2H50 C2H50 CH3 CH3 C2H5 nD :1~5171
4 C2U50 C2H50 D CH3 CH3 .~ I
(CH3)2N- (CH3)2N CH3 CH3 CH3
_
6 CH30 CH30 CH3 C2H5 CH3 nD :1.5203
7 CH30 CH30 C2H5 CH3 CH3 nD 1~5186
I .
8 CH30 CH30 (n)C4Hg CH3 CH3
~ l . I
g CH30 CH30 (n)C4Hg ~ CH3 C2H5 nD :1.5142
CH30 CH30 ~ CH2-l CH3 CH3 nD :1.5137
I r 1 I
11 C2H50C2H50 CH3 ' CH3 (n)C5H 1
I
12 CH30 ( 3)2 3 3 3
- 13 -
~7 5
Example 2
Insecticidal action: Spodoptera littoralis, Dysdercus
fasciatus and Ueliothis 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 Spodoptera littoralis or Heliothis virescens larvae in
the L3 stage or with Dysdercus fasciatus nymphs. Two plants
were used for each test compound and insect species.
Evaluation of mortality was made after 2, 4, 8, 24 and 48 hours.
The test was carried out at 24C and 60% relative humidity.
In this test, the compounds of Example 1 exhibited a positive
action against larvae of the species Spodoptera littoralis,
Heliothis virescens, and nymphs of the species Dysdercus
fasciatus.
Example 3
Insecticidal action: Pseudococcus citri
Plants (Vicia faba) which have been reared in pots and cut
back to a well-developed leaf-pair, were populated with
approx. 200 lice of the species Pseudococcus citri 24 hours
- 14 -
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 and evaluation
of mortality was made 4, 24 and 48 hours after the start of
the test.
In the above test, the compounds of Example 1 exhibited a
positive action against insects of the species Pseudococcus
citri.
Exam~ 4
., .
Systemic action against Aphis fabae
Bean plants which had well developed roots were transplanted
into pots containing 600 ccm of soil and then 50 ml of a
solution containing 50 ppm, 10 ppm or 1 ppm of the compound
to be tested (o~tained from 25% wettable powder) were p~oured
directly onto the soil.
After 24 hours the parts of the plants above the soil were
populated with aphids of the species Aphis fabae and a
plastic cylinder was then slipped over the plants
to protect the aphids from any possible contact with the test
substance either directly or via the gas phase.
The evalua~ion of mortality was made 48 and 72 hours
respectively after the start of the test. Two plants, ecch
~ ~ 5 ~
in a separate pot, were used per concentration of test
substance. The test was carried out at 25C and 70V/o relative
humidity.
In this te.st, compounds of Example 1 exhibited a positive
systemic action against Aphis fabae.
- 16 -
