Note: Descriptions are shown in the official language in which they were submitted.
~ ~ 3~ ~9
The present ~nventlon rela~es to novel dialkylthio
thiolophosphoryl ureas having pesticidal action, a process for
their manufacture and pesticidal compositions which contain them
as active principle, and a method of ~ontrolling pests which
comprises the use o the novel compounds.
Th~ dialkylthiolophosphoryl ureas have the formula I
- - .
C H O O O R
2 5 ~ " " / 2
P N~--C- N (I)
RlS R3
'`"' " ''' ':
wher~in Rl is a propyl or butyL group and each of R2 and R3 ~ -
independently of the other is a hydrogen atom or a Cl-C4-alkyl
group
The alkyl groups R2 and R3 can be b~anched or
straight-chain. SuitabLe examples of such groups are the
methyl, ethyl~ n-propyl, iso~propyl, n-butyl, iso-butyl and
8ec.butyl group.
Particularly preferred compounds on account o~
their action against pests, chiefly against phytoparasitic
nematodes as well as against insects and representatives of
the order Acarina, are those of the formula I wherein R~ ;
represents a n-propyl, iso-butyl or sec.-butyl group.
As nematocides, those compounds are preferred wherein
~ . ,
R2 represents a hydrogen atom, and, in particular, those com~
.
pounds wherein R2 represents a hydrogen atom or a methyl,
- 2 -
,
~. ~.......... .. . . .
~93~9
ethyl, n-propyl or iso-propyl group.
The compounds of the fonmula I, which are themselves
novel, are obtained by methods which are known per se, ~or ~ ~ .
example by reacting a compound of the formula II
P--N=C-0 (II) ~ .
RlS /
wherein ~ is as defined in formula I above, with a compound
of the form~la III - ~ . :
R2 ` `
N--H (III) . ~
R ~ :~
3 ~ ~ .
wherein R2 and R3 are as defined in formula I above.
The process is preferably carried ou~ at a reaction
temperature between 0 and 50C under normal pressure and in a :- .~
solvent or diluent which is inert to the react~s. Examples of ~ . .. -
suitable solvents or diluents are: ethers and ethen~L compounds,
such as diethyl ether, dLisopropyl ether, dioxan, dimethoxy
ethane and tetrahydrofuran; ketones, such as acetone and ethyl : .
methyl ketone; aliphatic, aromatic and h~ ogenated hydrocarbons, :
in particular benzene,.toluene~ xylenes, chloroform, chloro- :
benzene and methyLene chloride; as well as dimethyl ormamide~
dimethyl sulphoxide and hexamethylphosphoric triamides.
. - 3 ~
- ... ... . . - . .. . ~. , ~
~08~ 9
The compounds of the formula II used as starting
materials are partly known [see e.g. J.Gen.Chem. U.S.S.R. 36,
1439 (1966) and 39, 1480 (1969)] or they can be prepared
analogously to known methods.
The compounds of the formula I have a broadbiocidal
actlon and can be used for controlling a variety of pests
which are injurious to plants and animals, for example as
acaricides, insecticides, nematicides or bactericides. ~ `
The compounds of the formula I have, inter alia, a
notable systemic action on aphids (for example Myzus persicae
and Aphis fabae) and they also act well against paddy stem
borers (for example of the species Chilo suppressalis). .
Accordingly, they are suitable for controlling ornamental
plant pests and crop pests, chiefly in crops of vegetables, ;~
fruit r and rice.
, . . ~ ' '
However, the compounds of the formula I act primarily
against phytopathogenic nematodes among which may be men-
tioned the genera Meloidogyne, Radolphus, Pratylenchus,
Ditylenchus, Heterodera, Paratylenchus, Belonolaismus, Tri-
chodorus, Longidorus, Anguina and Aphelenchoides, and they ~ : .: ::
can be used for example to control phytoparasitic nematodes
in crops of sweet potatoes, coffee, teal cocoa, to~acco,
tomatoes and ground nuts. The concentration of active com- ~ :
pound for application to such crops is prefexably l to 8 kg
per hectare (wide area treatment).
, '
. .
- 4 ~
~ . . - : ~ . : , . -
' ' '- ., ' , ',:; ' ~ :
~33~69 :~
The pesticldal action can be substantlally broadened
and adapted to givencircumstances by the addition of other
pesticides. Examples of suitable additives lnclude: organic
phosphorus compounds, nltrophenols and derlvatives thexeof,
formamidines, ureas,pyrethroids;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. Suitable carrieræ 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 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 ; ~
conventional formulation which i5 commonly employed in ~ -
application technology.
The active compound isapplled in the form of solid
or liquid compositionsforcontrollingsoilnematodes. For
applicationto andworking intothe soil,those compositionsare
especially preferred which ensure auniformdistribution ofthe
active compound over a layer of soil which is15to 25cm deep.
The mode and form of application depend in particular on the
species of nematodes to be controlled, the climate, and the
- 5 -
' ,
'' - : ' . ' : '
.
'
. ~ ' .' . ~ " ' . '~
soil conditions.
The compositions according to the invention are
manufacturedinknown manner by homogeneously mixing and/or
grinding active substances of the formula I wlth thesuitable
carriers, with or without the addition of dispersants or
solvents which are inert to the active substances.
The active substances may be processed to the follow-
ing formulations: -
Solid formulations:
Dusts, tracking agents and granules ~coated-granules,
~,
impregnated granules and homogeneous granules).
Liquid formulations:
a) active substances which are dispersible in water:
wettable powders, pastes and emulsions;
b) solutions.
The content of active substance in the above des-
.. . .
cribed compositions is between 0.1% and 95%, but it must bementioned that higher concentrations can also be used if the
compositions are applied from an aircraft or other approp-
riate application devices.
The active substances of the formula I can, for
example, be formulated as follows ~throughout the present
specification all parts and percentages are by weight~: l
:
- 6 -
3~6~
;, .:
Dusts
-
The following substances are used to manufactur a) a
5% and b) a 2% dust: ` :
a)5 parts of active substance,
95 parts o~ talc; .
b)2 parts of active substance; ~ ..... ... .
1 part o~ highly disperse sillcic acid, ~ ~
97 parts of talc. ~ .
~; ~ '. ~",,' '
The active substances are mixed with the carriers ; . .:
and gro~nd.
Granules - :
The following substances are used to produce 5%
granules:
parts of active substance,
.
0.25 parts of epichlorohydr1n,
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 resul~
,: ~ .
tant solution is sprayed on kaolln, and the aceton i~ sub~
sequently evaporated in vacuo. Such microgranules are advan- !~
tageously used for controlling soll pe6ts (e.g. nematodea).
- 7
'
'- . ' . , . , , " ': ~' ' ., '
~U83~6~
''' ', ' ', .
Wettable powder~
The following constituents are used for the prepar-
ation of a) a 40~, b~ and c) a 25%, and d) a 10~ wettable
powder:
a) 40 parts of active substance,
parts of sodium lignin sulphonate,
1 part of sodium dibutyl-naphthalene sulphonate,
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 dibutyl naphthalene sulphonate,
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 cellulosemixture (1~
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin,
1;
- 8 ~
,
.. ;
1~3~6g '' "
d)10 parts of active substance,
3 parts of a mixture of the sodium salts of ;~
saturated fatty alcohol sulphates, ~:
5 parts of naphthalenesulphonic acid/formaldehyde ~:
condensate, ~ . .
82 parts of kaolln.
The active substances are homogeneously mixed, in ;::~
suitable mixers, with the additives, the mixture being then
ground in the appropriate mills and rollers. Wettable powders ~ ~ :
are obtained which can be diluted wlth water to give sus~
pensions o the desired concentration. .
Emulsifiable concentrates:
The following substances are used to produce a~ a
~. , . ,.:
10~, b) a 25%, and c) a 50% emul~aifiable concentrate~
a~ 10 parts of active substance,
3.4 parts of e~oxidised vegetable oil~
3.4 parts of a combination emulsifier consistlng o
fatty alcohol polyglycol ether and alkylaryl~
: sulphonate calcium salt, :~
::~ 40 parts of dimethyl formamide,
::
: : ~ 43.2 part of xylene;
.
- ~ . . . .
-. .- : : . : ~ : ~
,:.. ' ' : : ' ' ,, ' ' ' . ~ ': ' , ":
, . . , ~ ~ :
~ ~3.
b~25 parts of ac~ive substallce,
2.5 parts o~ ~poxidlsed vegctable oil,
parts oE alkylarylsulphonate/fatty alcohol
polyglycol ether mixture,
S parts of dimetllyl formamide,
57,5 parts o xylene;
c)50 parts of activP 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.
~' ~,
The ~ollowing ingredients are used to prepare a) a
5% spr~ly, and b) a 95% spray:
a~5 parts o active substance,
-1 part of epichlorohydrin~
94 parts of ligroin (boiling range 160 190C);
b)95 parts o~ active substance,
par~s of epichlorollydrin.
The invention is ~urther illustrated by the
following ~xamples.
- 10
' ''. ~ ~
. . :: . - . , : : :
... . : .. :: ~ .. : .
: .
~8316g
Example 1
Preparation of 0-ethyl-S-n-propyl-thiolophosph~yl urea
Ammonia is introduced at a temperature of 20C into
a solution of 30.3 g of 0-ethyl-S-n-propyl-thiolophosphoryl
lsocyanate in 250 ml of abs. ether until the solution is
saturated. The precipitate which forms is collected with
suction. Recrystallisation of ~he precipitate from methano
yields the product of the formula
~'
n~:3H7S\ O ,. ,~
/P--NH--CO--NH2 m.p. 191 -194 C
C2U50 , ''
(compound 1)
The following compounds of the~formula I are also
obtained in analogous manner~
C2 5 ~" ,, / 2
~N~N (I )
RlS / 3
~:
' "' ' `' ' ' ' ''
': ' ~ ' , '
,
, . ' . . ~ ,
~3~9
.... ~ .. . . .
Compou~ Rl R2 R3 Physical data ~
. _ .. .. . _ . .
. (n)C3H7 H CH3 m.p. ~~ 105-107 C
_ _ , . .
3 (n)C3H7 H C2H5 m.p._ 92-95 C
....... , .~...................................... _ .
4 . (n)C3H7 (n)C3H7 m,~~.~~95-97 C
(n~C3H7 H (i)C3H7 m,~.98~102 C .
_
(n)C3H7 (n)c4H9 m,p. 72-74C .
7 (n)C3H7 CH3 CH3 nD: 1,5024
. ~
8 (n)C3H7 C2H5 C2H5 . n20 1,4941
9 (n)C3H7 (n)C4Hg (n)C4Hg n20: 1,4851 !
. _
(sek.)C4Hg M H ~ ~ -166-168 C~
.
11 (Sek.)c4H9 C 3 m .- 138-139C
12 (n)C4Hg _ ~ H m.p.186-187C
,
13 (n)C4Hg H m-.p.~ 87-92 C -~
14 (;)C4Hg H H m p.~ 172-174C
. . _ _ . ., ~
15 (i)C4H~ H CH3 m.p.~ 99-101C L~
.
.~`', '' ' ,'' .
~' '. :.
- 12 -
: ' - , ', ''- ', :' : ' ~ ' ' ; '
. : . . : ?
.... .. ! , ' .
, ' ' ' ' ' . . ' ' '
' " , ', . ..
' ' ' ' ' ,"' . ' ' ' " ' . ' :' ' ' ' ' ' ' ' ' ,, ,, ' ' ' ' ; . '
,, ~: ' . ~ ' ' . ~ :
~ 3~
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_ample 2
.
Ins ec t iGi~
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
containing 800, 200 or 100 ppm of the active compound to be
tested. l'hen each pot was populated wi~h 5 Chilo suppressalis
larvae in the L2-stage and the treated plants were subse- ,~
quently replaced in the pots on top of the larvae.
' One plant wa~ 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 l exhibited
a positive action against Chilo suppressalis.
Compounds 2 to 5, 8, 10 to 12 and 14 are to be
singled out on account o~ their particularly good action , ~ '~
(100 % kill at 100 ppm). ,
Example 3
System aggopst A~his fabae/M~y~s persicae
Bean plants which had grown roots were transplanted , - -~ '
into pots containing 600 ccm of soil and then 50 ml of a
solution of the compound to be tested (obtained,from ~5 ~/0
wettable powder) were poured directly onto the soil in a
, - 13 -
~:
, . ,. . - . - - - - ~ ,
, ~ :
,
~ 331~i9
concentration of 50 ppm or 10 ppm.
After 24 hours the parts of ~he plants above the soil
were populated with aphids of the species Aphis fabae or
Myzus persicae and a plastic cylinder was then slipped over
the plants to protectthe aphids from any possible contact with
the test substance either directly or via the gas phase.
The evaluation of mortality was made 48 and 72
hours respectively after~he start of the test. Two plants, each
in a separate pot, were used per concentration of test substance.
The test was carried out at 25C and 70 % relative humidity.
In this test, compounds 1 to 5, 8 and 10 to 15 of
Example 1 exhibited a good systemic action against Aphis
fabae and Myzus persicae. Compounds 2, 5, 10 to 12, 14 and 15
are to be singled out on account of their particularly good
action (100 % kill after 48 hours at 10 ppm). ;
xample 4
ematicidal action a~ainst Meloidogyne inco~nita
To test the action against soil nematodes, the test
compound was homogeneously mixed in a concentration of
10 ppm with soil or sand infected with root gall nematodes
(Meloidogyne incognita)O Immediately afterwards, ~oung
tomato plants on the one hand and young tobacco plants on the
other were planted in the thus prepared soil, Three parallel
.
tests were carried out under the corresponding conditions ~
~ ` : ',
- 14 - ~
.
1083~g
~species o plant/type of soil~.
Compounds 1 to 5~ 10, 11, 14 and 15 of Example 1
exhiblted a good action in this test ~only slight to very
slight attack determined). Compounds 1 and 2 are to be
singled out on account of their particularly good action,
Example 5
Acaricidal action a~ainst TetranYchus urticae (OP-sensitive)
and Tetranychus cinnabarius (OP-tolerant)
The primary leaves of Phaseolus vulgaris plants `~
were infected with a infested piece of leaf from a mass culture
of Tetranychus urticae (OP-sensitive) or Tetranychus~cinnaba-
rius (OP-tolerant). (The tolerance refers to the tolerance to ;~
diazinone). The treated plants infested with the mobile stages ~
which had migrated to the plants were sprayed dripping wet with ~ ~-
a test solution containing 400 or 200 ppm of the compound to ~
.
be tested. The number of living and dead adults and larvae ~ -
:,, :,
(all mobile stages) was evaluated under a stereoscopic
microscope after 24 hours and again after 7 daysO One plant ~as
used for each test substance and test species. During the test
run~ the plants stood in greenhouse compartments at 25 C. '
In the above test, the compounds of Example 1
exhibited a positi~e action against adults and larvae o ~e ~e~s
Tetranychus urticae and Tetranychus cinnabarius.
- 15 -
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