CA1045149A - Esters - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Phosphorus compounds of the formula

Description

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The present invention provicles organic phosphorus compounds, processes for their manufacture, and a method of using them in pest control.
The phosphorus compounds according to the invention have the formula ~ ~P I

(R4)m ( 3)n wherein Rl represents alkyl with 3 to 7 carbon atoms, R2 represents methyl or ethyl, R3 and R4, independently of one another, represent a nitro group or a halogen atom, m = O or an integer from 1 to 5 inclusive and n = O or ~ -an integer from 1 to 4 inclusive, and X represents oxygen or sulphur. -Halogen is to be understood as meaning fluorine, chlorine, bromine and/or iodine. Chlorine and/or bromine are preferred.
The alkyl groups represented by Rl can be straight-chain or branched. Examples of such groups include: n-propyl, n-butyl, iso-butyl, sec. butyl and tert. butyl, n-pentyl, n-hexyl, n-heptyl and isomers thereof.
Preferred compounds on account of their action are those of the formula I wherein Rl represents n-propyl-iso-propyl, n-butyl, sec.
butylJ n-pentyl or n-heptyl, R2 represents ethyl, R3 and R4 each repre- ~ `~
sents chlorine, bromine and/or ni*ro, m and n are each 0, 1 or 2 and X ~ -represents oxygen or suIphur.
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~0451~91 The compounds o the ormula I can be manufactured by the following methods which are known pe~ se;
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P-Cl -I HO ~ O ~ acid acceptor ~ ~

(R3)h ~ 4)m . :.
~II) ~III) -,, , ,-:. , , lb) '. .~ ~. :, X -P-Cl + MeO ~ O ~ - > I

(R3)n ~ 4)m ~. ;
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2) 2 \¦¦ ~ ~ acid acceptor .
/ P-Cl ~ HO ~ O ~
Cl:: ~R3)n ~ ~ m , :

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R O 11 ~

Cl ~ ~ ~ HSRl ~acld acceptor : ~R3)n (R4)m ~IIIa) VI) + MeSR

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:1~4S~4~ -In the formulae II to IV~ the symbols R1 to R4, m and n and X have the same meanings as ~or the formula I and Me represents an alkali metal, in particular sodium or potassium, or represents the group (R)3NH, wherein R represents hydrogen or alkyl with 1 to 4 carbon atoms.
Suitable acid acceptors are: tertiary amines, e.g. trialkyl-amines, pyridineJ dialkyl anilines; inorganic bases, e.g. hydrides, hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals. It is sometimes necessary to use catalysts in the reactions e.g. copper or copper chloride. Processes la, lb and 2 are carried out at a reaction temperature between -2C and +130C, at normal pressure, ~ -and in solvents or diluents. ; ~ :
~xamples suitable solvents or diluents are: ethers and ethereal compounds, e.g. diethyl ether, dipropyl ether, dioxan, tetra-hydrofuran; amides, e.g. N,N-dialkylated carboxy amides; aliphatic, aro-matic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform, chlorobenzene; nitriles, e.g. acetonitrlle; dimethyl sulphoxide, ketones, e.g. acetone, methyl ethyl ketone; water.
~ The starting materials of the formulae II, III, IV and V
are known and can be manufactured in analogous manner to known methods.
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The compounds of the formula I exhibit a hroad biocidal : :
activity and can be used for the control of a variety of plant and animal pes~s.
In particular they are suitable for combating insects of th~ families~
Acrididae, Blattidae, Gryllidae, GryllotalpidaeJ Tettigoniidae, Cimi- :
cidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelisae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, TenebrionidaeJ Curulionidae, Tineidae, Noctuidae, Lyman- ` .
triidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Mus-cidae, Calliphoridae, Trypetidae, Pulicidae as well as Acaridae of the ,.-: :-families: Ixodidae, Argasidae, Tetranchidae, Dermanyssidae. ~-By addition of other insecticides and/or acaricides it , ~ :
is possible to improve substantially the insecticidal or acaricidal . ~:
action and to adapt it to given circumstances. .: .
Examples of suitable additives are: organic phosphorus ~ -compounds, nitrophenols and derivatives thereof; formamidines; ureas; ;~~
carbamates and chlorinated hydrocarbons.

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1(~45149 : ~-The compounds of the formula I may be used as pure ~-~
active substance or together with suitable carriers and/or àdditives.
Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technologyJ for ;
example natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fer~ilisers.
For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions9 sprays, to solutions or suspensions, in the conventional formulation ~ ~
which is co =only employed in application technology. Mention is ~ ~;
also to be made of cattle dips and spray races, in which aqueous pre~
parations are used. j~ ;

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Th~ agents according to the invention are manufactured . in known manner by intimately mixing and/or grinding active sub-stances of the formula I with the suitable carriers, optionally . .
with the addition of dispersants or solvents which are inert to-wards the active substances. The active substances can take, and :
be used in~ ~he following forms: .
Solid forms:
dusts, tracking agents, granules, coated granules impregnated granules and homogeneous granules.
- 10 Liquid forms~
-. a) active substances which are dispersible in water:
wettable powders, pastes, emulsions: :.
b) solutions. ~ ^
The content of active substance in the above described agents is between 0.1% to 95%, in which connec~ion it should be `.!.. ',,,,,,;,,~.'.
mentioned that, in the case of application from aircraft or some other suitable means of application,.it is possible to i use concentrations of up to 99.5% or even pure active substance. ..
The active substances of the formula I can, for example, ~ ;
be formulated as follows:
Dusts The following substances~are used to manufacture ~ :
a) a 5% and bj a.2% dust~
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a) 5 parts of active substance 95 parts of talcum b) 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum.
The active substances are mixed with the carriers -and ground.
Granules .. . . :
The following substances are used to produce 5%
granules:
S 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 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 resulting solution is sprayed on kaolin, and the acetone is subsequently evaporated 2Q in vacuo.
' ett:able poNdeT. ~' The following constituents are used for the preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
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a) 40 parts of active substance, parts of sodium lignin sulphonate, 1 part of sodium dibutyl-napthalene sulphona~e, 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 napthalene . ~
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 cellulose mixture (1~
8.3 parts of sodium alum mium silicate, 16.6 parts of kieselguhr, ~. ;
;~ 46 parts of kaolin.

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The active substances are intimately 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 with water to give suspensions of any desired concentration.
Emulsifiable concentrates:
The following substances are used to produce a) a 10%
and b) a 25% emulslfiable concentrate: ~
: a) 10 parts of active-substance 3 `; `.
3.4 parts of epoxidised vegetable oil, ~ :
:13.4 parts of a combination emulsifier consisting of :~
fatty alcohol polyglycol ether and alkylaryl ...
~ sulphonate calcium salt, 20~ 40 par~ts oP dimethylformamide, 43.2 parts of:xylene, 25 parts of actlve substance,: `
2.5 parts~of epoxidised vegetable oil, : .~:~
: 10~ parts of an:alkylarylsùlphonate/fatty alcoholg~lycol ether mixture, ~ ` ;

5 parts of dimethylformamide, ; : :
57.5 parts o xylene.~

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From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.
Spray:
The following constituents are used to prepare a 5% spray:
5 parts of active substance, 1 part of epichlorohydrin, 94 parts of benzene (boiling limits 160C-190C).
Example 1 With stirring, 41 g of 0-ethyl-S-n-propylthiophosphoric chloride in 60 ml of diethyl ether is added dropwise so rapidly to a solution, cooled to 10C, of 37 g of 4-hydroxydiphenyl ether and 22 g of ~riethylamine in 500 ml of absolute diethyl ether that the temperature does not rise above 30C. The reaction mixture is stirred for a further 2 hours at 20-30C and treated, with continued stirring, with 300 ml of ice water. The organic phase is isolated, shaken once with water and twice with ice cold 5% -sodium hydroxide solution and then washed neutral with water.
The ethereal phase is treated with activated chàrcoal, filtered, dried, and'the-solvent is~'evaporated off. The oily residue is dried for 3 hours at 70C and 0.1 Torr to yield the compound of the formula ~
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as a yellowish, non-distillable, viscous oil with a refraction of nD = 1.5524.
The following compounds are also manufactured in analogous manner:

O2N ~ o ~ ll OC2H5 nD ~ 1,5761 I SC3H7(n) nO = I,5650 - N2 , . ~."
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~ ~ SC3H7~-) nO = 1,5~75 ~ ~

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--O _~ O b ~ 2 5 nD = 1, 5476 sc5Hll (n) . -OC H nD20 ~ l,5561 :

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0 ~--O-P \ nD = 1~ 5 3 85 , ' ' !

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,~. oc ~ o Cl-~ 0 _~_ P~ 2 5 n20 ~ 1, 5550 3 7 ( n ) ~0 ~3_0 p C2H5 nD = 1, 5679 Cl 3 7 (n) :: .
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~SC3H7( ) n20 = l,56~3 Br Cl~ ~) SC3S7 ~ ) nD = 1 5752 Br Br~)_ O ~_ 0 _ p OC2~5 n20 = 1 6039 Br sc3H7 ( ) n : - :
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~. ' ~045149 Example 2 A) Insecticidal ingest poiso~ action Cotton and potato plants were sprayed with a 0.05% aqueous emulsion ~obtained from a 10% emulsifiable concentrate). After the coat-ing had dried, the cotton plants were populated with Spodoptera littoralis or Heliothis virescens larvae L3 and the potato plants with Colorado potato beetle larvae ~Leptinotarsa decemlineata). The test was carried out at 24C and 60% relative humidity. In the above test, the compounds accord-ing to Example 1 displayed good ingest poison action against Spodoptera ~-littoralis. Heliothis and Leptinotarsa decemlineata larvae. ~ ~

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Example 3 Action against Chilo suppressalis Six rice plants at a time of the variety Caloro were transplanted into plastic pots (diameter at the top = 17 cm) and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (Ll: 3 - 4 mm long) took place 2 days after the active substance had been applied in granule form to the paddy water (rate of application: 8 kg of ac~ive substance per hectare).
Evaluation of the insecticidal action took place 10 days after application of the granules. The compounds according to Example 1 were active in the above test against Chilo suppressalis.
Example 4 Sterilised compost earth was homogeneously mixed with a wettable powder containing 25% of active substance so that there resulted a rate of application of 8 kg of active substance per hectare.
Young zucchetti plants (Cucumis pepo) were put into plastic pots with the treated soil (3 plants per pot; diameter of pot = 7 cm). Each pot was infected immediately afterwards with 5 Aulacophora femoralis and Pachmoda ;
or Chortophila larvae. The control was carried out 4, 8, 16 and 32 days after . , .
depositing the larvae. ~
At 80 - 100% kill after the first control, a fresh infestation with ~ -5 larvae each was carried out in the same soil sample with 3 new zucchetti plants. If the activity was less than 80%, the remaining larvae remained in the soil sample until the control immediately following. If an active sub-stance at a rate of application of 8 kg/ha still effected a 100% kill, a further control with 4 and 2 kg of active substance per hectare was carried out.
In the above test,-the compounds according to Example 1 displayed action against Aulacophora femoralls, Pachmoda and Chortophila larvae. `-Example 5 Action against~ticks A) ~ picephalus bursa Five adult ticks and 50 tick larvae were counted into a glass tube -~16 -'~,'. ' ', 1~4~
and immersed for 1 to 2 minutes in 2 ml o an aqueous emulsion from an emul-sion series each containing 100, 10, 1 or 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion could be absorbed by the cotton wool.
In the case of the adults evaluation took place after 2 weeks, and :
in that of the larvae after 2 days. Each test was repeated twice.
B) Boophilus microplus ~larvae) Tests were carried out in each case with 20 OP-sensitive larvae using a dilution series analogous to that of test A. ~The resistance refers to the tolerability of Diazinon). The compounds according to Example 1 acted in these tests against adults and larvae of Rhipicephalus bursa and sensitive and OP-resistant larvae of Boophilus microplus.
Exam~le 6 , .
Acaricidal action Phaseolus vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of Tetranychus urt1cae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated are sprayed with the emulsified test preparations form a chromatography atomiser so that thé spray broth does not run off. The number of living and dead 2D larvae, adults and eggsare evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the "interim", ; the treated plants are kept in greenhouse compartments at 25C. The compounds according~to Example l were active in the above test against eggs, larvae and adults of Tetranychus urticao.
-EXample 7 Action against soil nematodes To tho test action against soil nematodes~ the active substance in the concentratlon indicated in each case is applied to an~ intimately mixed with soil~infected with root gall nematodes (Meloidgyne Arenaria). Immediate- ;
30: ly afterwards, tomato cutt m gs are planted in ~he thus prepared soil in a ~ -' s series oftes*s and after a walting time of 8 days tomato seeds are sown in another test serles. ~;

~ ''''' ' In order to assess ~he nematocidal action the galls present on the roots are counted 28 days after planting iand sowing respectively. In this test the compounds according to Example 1 display good action against .-Meloidgyne arenaria.

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Claims (18)

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

1. A compound of the formula I

(I) wherein R1 represents an alkyl group having from 3 to 7 carbon atoms, R2 represents a methyl or ethyl group, R3 and R4, independently of one another, represent a halogen atom or a nitro group, m represents 0 or an integer from 1 to 5 inclusive, n represents: 0 or an integer from 1 to 4 inclusive, and X represents oxygen or sulphur.

2. A compound according to claim 1, wherein R1 represents an n-propyl, i-propyl, n-butyl, s-butyl, n-pentyl or n-heptyl group.

3. A compound according to claim 1, wherein R1 represents an n-propyl group and R2 represents an ethyl group.

4. A compound according to any one of claims 1 to 3, wherein R3 and R4, independently of one another represent a chlorine or bromine atom or a nitro group, and m and n, independently of one another represent 0, 1 or 2.

5. A compound according to claim 1, of the formula .

6. A compound according to claim 1, of the formula .

7. A compound according to claim 1, of the formula .

8. A compound according to claim 1, of the formula .

9. A compound according to claim 1, of the formula .

10. A compound according to claim 1, of the formula .

11. A compound according to claim 1, of the formula .

12. A compound according to claim 1, of the formula .

13. A compound according to claim 1, of the formula .

14. A compound according to claim 1, of the formula .

15. A compound according to claim 1, of the formula .

16. A compound according to claim 1, of the formula.

.

17. A compound according to claim 1, of the formula

18. A method of controling pests of the Class Insecta or of the Order Acarina at a locus, which method comprises treating said locus with a compound as claimed in any one of claims 1 to 3.