CA1083169A

CA1083169A - Dialkylthiolophosphoryl urea pesticides

Info

Publication number: CA1083169A
Application number: CA277,121A
Authority: CA
Inventors: Odd Kristiansen; Jozef Drabek
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1976-04-29
Filing date: 1977-04-27
Publication date: 1980-08-05
Also published as: FR2349594A1; GB1539698A; IL51965A0; NL7704554A; FR2349594B1; JPS52133927A; DE2718554A1

Abstract

Abstract of the Disclosure Compounds of the formula I

Description

~ ~ 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, , ~. ~.......... .. . . .

~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.

' ''. ~ ~

. . :: . - . , : : :
... . : .. :: ~ .. : .
: .

~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~
.

.~`', '' ' ,'' .
~' '. :.

: ' - , ', ''- ', :' : ' ~ ' ' ; ' . : . . : ?

.... .. ! , ' .
, ' ' ' ' ' . . ' ' ' ' " , ', . ..
' ' ' ' ' ,"' . ' ' ' " ' . ' :' ' ' ' ' ' ' ' ' ,, ,, ' ' ' ' ; . ' ,, ~: ' . ~ ' ' . ~ :

~ 3~
;' ~ '.
_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.

':

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PRIVILEGE
OR PROPERTY IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula I

(I) wherein R1 represents a propyl or butyl group and each of R2 and R3 independently of the other represents a hydrogen atom or a C1-C4-alkyl group.

2. A compound as claimed in claim 1 wherein R1 represents an n-propyl, isobutyl or sec.-butyl group.

3. A compound as claimed in claim 2 wherein R2 represents a hydrogen atom.

4. A compound as claimed in claim 3 wherein R3 represents a hydrogen atom or a methyl, ethyl, n-propyl or isopropyl group.

5. O-ethyl-S-n-propyl-thiolophosphoryl-urea as claimed in claim 4.

6. N-(O-ethyl-S-n-propyl-thiolophosphoryl)-N'-methyl-urea as claimed in claim 4.

7. N-(O-ethyl-S-n-propyl-thiolophosphoryl)-N'-ethyl-urea.

8. N-(O-alkyl-S-n-propyl-thiolophosphoryl)-N'-n-propyyl-urea.

9. N-(O-ethyl-S-n-propyl-thiolophosphoryl)-N'-isopropyl-urea.

10. O-ethyl-S-sec.-butyl-thiolophosphoryl-urea.

11. N-(O-ethyl-S-sec.-butyl-thiolophosphoryl)-N'-methyl-urea.

12. O-ethyl-S-isobutyl-thiolophosphoryl-urea.

13. N-(O-ethyl-S-isobutyl-thiolophosphoryl)-N'-methyl-urea.

14. A method of controlling pests which method comprises applying to said pests or their locus a compound as claimed in claim 1.

15. A method as claimed in claim 14 wherein the pests are insects which cause damage of plants.

16. A method as claimed in claim 14 wherein the pests are plant pathogenic nematodes.

17. A method as claimed in any one of claims 14 to 16 wherein, in the compound of the formula I, R1 represents an n-propyl, iso-butyl or sec.-butyl group.

18. A method as claimed in any one of claims 14 to 16 wherein, in the compound of the formula I
R1 represents an n-propyl, isobutyl or sec.-butyl group, R2 represents a hydrogen atom, and R3 represents a hydrogen atom or a methyl, ethyl, n-propyl or isopropyl group.