CA1051915A

CA1051915A - Esters

Info

Publication number: CA1051915A
Application number: CA153,177A
Authority: CA
Inventors: Ernst Beriger; Jozef Drabek
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1971-10-12
Filing date: 1972-10-04
Publication date: 1979-04-03
Also published as: IT986856B; MY7700160A; JPS4844434A; DD101541A5; DE2249462B2; FR2156230A1; FR2156230B1; IL40476A; GB1417116A; BE789937A; DE2249462A1; AR195503A1; NL161157C; IL40476A0; SU673138A3; NL7212564A; OA04201A; KE2694A; ES407515A1; CY887A

Abstract

Abstract of the Disclosure Organic phosphoric acid derivatives of the formula

Description

105~9il5 This invention relates to organic phosphoric acid derivatives, their manufacture and their use in pest control.
According to the present invention there are provided compounds of the formula O X
/ ~ ~Br (I) (n)C3H7S y wherein X is hydrogen and Y is chlorine, or X is chlorine and Y is bromine.
The compounds of formula I can be made by the following known processes:

-2-~, ,A .
.

1~519iS

~)C21~50 1l (n)C3H7s> + H~Bracid tbindi g ~3, I
(II) (III) lb~>:P Cl + Me~Br > I

(II) . (IV) 2 ) 2 5 11 Cl> ~HO~r >
(V) (III ) Cl> ~ + I~SC3H7(n) ACiC bindin~

3 7 ( ) >
(VI ) (VIII ) ~0~1915 x C2H50 S /~<
3a) P-O ~\ ~ Br + (R)3N
2 5 ~

(IX) (X) ~7~3 ~o S ,~
C2H50 ~ Hr ~ (n)C3H H~

(XI) (XII) X
C2H5 S ~ S (XIII) (XII) :~
3b) P-O ~\ / ~ Br + ROC - SMe + (n) C2H50 ~ or MeSR (XIV) y or Me2S
(IX) or MeSH
S

~ or (RO)2P - SMe (XV) ~.
~ /

~051915 In the Formulae III, IV, and VI to XV, X and Y have the meanings given for Formula I and Me represents an alkali metal7 particularly sodium or potassium, ammonium or alkylammonium, R represents Cl-C4 alkyl, such as methyl or ethyl and Hal represents a halogen atom such as chlorine, bromine or iodine.
As acid binding agents there can be used: tertiary amines, e.g. trialkylamines, pyridine, dialkylanilines; inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of aIkali and aIkaline earth metals. It is sometimes desirable in the reactions to use catalysts, such as e.g. copper or copper chloride. The processes la and lb, 2 and 3a and 3b are carried out at a reaction temperature between 0 and 130C, at normal pressure and in solvents or diluents inert to the reactants.
The following are, ~or example, suitable as inert solvents or diluents: ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, tetrahydrofurane; amides such as N,N-diaIkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, particularly benzene, toluene, xylene, chloroform, chlorobenzene; nitriles such as acetonitrile; DMS0. For processes 3a and 3b alcohols are also suitable.
The starting materials of Formula II can be made by methods analogous to those described for example in J. Qrg. Chem. 30,3217 (1965).

~_~`J I

1~5~91S
Compared to similar compounds known from Swiss Patent Specification No. 414,597 and British Patent Specification Nos. 1,295,418; 1,214,188 and its Patent of Addition, Serial No. 1,311,733 the compounds of Formula I show surprisingly better insecticidal action, particularly against stored product and household pests, and a more suitable toxicity for this useO As well as this, the effectiveness of the compounds according to the invention extends over all development stages, such as eggs, larvae, nymphs, pupae and adults of insects of the families:
Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as Acarina of the families Ixodidae, Argasidae, Tetranychidae and Dermanyssidae O
The insecticidal and/or acaricidal action can be substantially broadened and matched to given circumstances by the addition of other insecticides or acaricidesO Such additional " active ingredients may be selected from the group of organo phosphorus compounds; nitro phenols, and derivatives thereof;
ureas; carbamates; chlorinated hydrocarbons, pyrethrinlike com-pounds; and amidines, especially formamidines, a most useful representative of which is l,l-dimethyl-2-(2'-methyl-4'-chloro-phenyl)-formamidine~

lO~91S
The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or addi-tives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formu-lation technique such, for example, as solvents,dispersants, wetting agents, adhesives, thickeners, binders and/or ferti-lisers.
For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dis-1~ persions, sprays~ to solutions~ or suspensions in the conven-tional formulation which is commonly employed in application terminology. Mention may also be made of "cattle dips" and spray races", in which aqueous preparations are used.
me agents according to the invention are manufactur-ed in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optional-ly with the addition of dispersants or solvents which are inert towards the active substances. me active substances may be available and can be used in the following forms:
Solid forms _ _ 105~9~5 Dusts, scattering compositions, granules (coated granules, impregnated granules and homogeneous granules).
Liquid forms:
(a) active substance concentrate disperSible in water:
wettable powders, pastes, emulsions;
(b) solutions.
To manufacture solid forms (dusts, scattering compositionsJ, the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, an~onium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used alone or in admixture with one another.
Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, SiO2, granicalcium, bentonite etc and then evaporating the solvent.
Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/-` formaldehyde; dicyandiamide/formaldehyde;

:~ ' ~.~1 lOS19lS
melamine/formaldehyde or others~, whereupon a mild polymerisa-tion is carried out that does not affect the active substances and in the proce~s of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, poly-acrylonitrile~ polyester or others) which have a specific sur-face area and a favourable predeterminable adsorption/desorp-tion ratio,with the active substances, for example in the form of their solutions (in a low boil;ng solvent) and to re-move the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 ~litre to 600 g/
litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.
It is also possible to obtain granules by compact-ing the carrier with the active substance and carriers and subsequently comminuting the product.
To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, whioh for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following:
olein/chaIk mixture, cellulose derivatives (methyl cellulose, ;~
carboxymethyl cellulose), hydroxyethyl glycol ethers of mono-_g_ lOS19lS
alkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the aIkyl radlcal, lignin sul~onic acids, their aIkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, con-densation products of urea and formaldehyde, and also latex products.
The water-dispersible concentrates of the active substance, i.e~ wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substance and anti-foam agents and, optionally, solvents.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Carriers are, for example, those mentioned for the solid forms of application. In SQme cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene lOSl~lS
or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, aIkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfated hexa-decanols, heptadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of o]~l methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.
Suitable anti-foam agents are silicone oils.
The active substances are mixed, ground, sieved and strained with the additives mentioned above that, in wettable powder, the solid particle size of from 0.02 to 0.04 and in pastes of 0.03 mm is not exceeded. To produce emulsifiable con-centrates and pastes, dispersing agents such as those cited above, organic solvents and water are used. Examples of suitable solvents are the following: alcohols, benzene, xylenes, toluene, ` dimethyl sulfoxide, and mineral oil fractions boiling between 120 and 350 C. The solvents must be practically odourless, not phytotoxic~ inert to the active substances.
Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of the general fonmula I are dissolved in suitable organic solvents, mixtures ~05191 ~i of solvents or in water~ Aliphatic and aromatic hydrocarbons~
chlorinated derivatives thereof, aIkyl naphthalenes, and mineral oils alone or mixed with each other~ can be used as organic solvents.
me content of active substance in the above described agents is between 0.1% to 95%, in which connection it should be mentioned that in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations~ofup to 99.5% or even pure active substance.
m e active substances of the formula I can, for ex-ample, be formulated as follows:
Dusts .
The following substances are used to manufacture a) a 5% and b) a 2% dust:
a) 5 parts of active substance 9S parts of talcum b) 2 parts of active substance 1 part of highly disperse silica 97 parts of talcum The active substances are mixed with the carriers and ground.
Granules me following substances are used to produce 5% granules:
5 parts of active substance 0.25 parts of epichlorohydrin 0.25 parts of cetyl polyglycol ether 105~91S
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 thus obtained solu-tion is sprayed on to kaolin, and the acetone subsequently evapo~rated in vacuo.
Wettable powder me following Constituents are used for the preparation of lOa) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance 5 parts of sodium lignin sulphonate 1 part of sodium dibutyl-naphthalene sulphonate 54 parts of silica acid.
b) 25 parts of active substance

4.5 parts of calcium lign;n sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1) 1.5 parts of sodium dibutyl naphthalene sulphate 19.5 parts of silica acid 19.5 parts of Champagne chalk 28.1 parts of kaolin.
c) 2S parts of active substance 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture 8.3 parts of sodium aluminium silicate lOSl91S
16.5 parts of kieselgur 46 parts of kaolin.
d) 10 parts of active substance parts of naphthalenesulphonic acid/formaldehyde condensate 82 parts of kaolin.
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 suspenslons of any desired concentration.
Emulsifiable concentrates:
The following substances are used to produce a) a 10% and b) a 25% 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 40 parts of dimethylformamide 43.2 parts of xylene.
b) 25 parts of active substance 2.5 parts of epoxidised vegetable oil 10 parts of an alkylarylsulphonate/fatty alcohol-polyglycol ether mixture

5 parts of dimethylformamide 57.5 parts of xylene.
From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.

'~i ~ ~ - 14 -~ "

lOSl91S
Spra~s The following substances are used to manufacture a 5% spray:
5 parts active substance 1 part epichlorohydrin 94 parts petrol (boiling range 160-190C).
The following exanples illustrate the manufacture and testing of the compounds according to the present invention.
ample 1 Manufacture of the compound n~C3H75> ~}

Cl 31.1 g (0.15 mole) 2-chloro-4-bromophenol were dissolved in 150 ml benzene and 15.1 g triethylamine were then added. At 10-15C, 32.0 g of O-ethyl-S-n-propylchlorothiophosphate were added dropwise with continuous stirring. Stirring was then continued for 12 hours at room temperature.
Ihe mixture was washed with water, 3% Na2C03 solution and water and dried over anhydrous sodium sulphate. me benzene was distilled off and the residue purified by distillation (at 130C/0.01 torr).
49 g of the ester of the above formula was obtained with a refractive index ~ 1.5466.
me following compound was made in analogous fashion:

2 5 \ Il ~ 24 (n)C3H7s ~ ~ Br nD 1.5719 Br ~.. , . . ~ .

: . :

lOS1~15 E~c~Dle 2 A) Insect~cidal inFest ~oisor. action Tbbacco and potato plants .rere sprayed with a 0.05% aqueolls e~ulsion (obtained from a 10% emulsifiable concentrate).
After the coating had dried, E~yptian cotton leaf worms (3podoptera littoralis) were settled on the tobacco plants and Colarado potato beetle larvae (Leptinotarsa decemlineata) on the potato plants. Ihe test t~as carried out at 24C and 60% relative h~idity.
The compounds according to Example 1 had an ingest poison lQ action against Spodoptera littoralis and Leptinotarsa decemaineata in the above test.
B) Systemic insecticidal action To determine the systemic action, rooted bean plants (Vicia faba) were put into a 0.01% aqueous active substance solution (obtained from a 10% emulsifiable concentrate). After 24 hours, aphids (Aphis fabae) ~ere placed on the parts of the plant above the soil. The aphids were protected from contact and gas action by means of a special device. The test was carried out at 24C and 70% relative humidity. In the above test the compounds according to Example I displayed a systemic action against A~his fabae.
Example 3 Action a~ainst Chilo suppressalis Six rice plants at a time of the variety Caloro were trans-pl~nted into plastic pots (dic~.eter at the top = 17 cm) and reared to a hei~h.t of about 60 cm. Infestation with Chilo suppressalis larvae (Ll;
3-4 .~ lon~) took place 2 days after lOSl91S
application of the active substance in granule form to the paddy water (rate of application: 8 kg of active 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 Pachnoda 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 carr~ed 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 substance 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 Exa~lple 1 displayed action against Aulacophora femoralis, Pachnoda and Chortophila larvae.

Example 5 Acaracidal action Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action. m e occupying mobile stages were sprayed with the emulsified test preparations from a chromatography atomiser so that the spraying preparation did not run off. The number of living and dead larvae, adults and eggs were evaluated after 7 days under a stereoscopic microscope and the results expressed in percentages.
During the '`interim", the treated plants were kept in greenhouse compart-ments at 25C.
The compounds according to Example I were active in the above test against eggs, larvae and adults of Tetranychus urticae.

lj' .' L~

10519~5 Example 6 Action aRainst household and stored product pests _ . _ A dust on a base of talcum and containing 5% active substance was applied to filter paper in concentrations of 200, 100, 50, 25 and 12.6 mg active substance per m2. Onto each of the treated substrates were applied 5 Periplaneta americana, Dermestes frischii, Tribolium confusum and Oryzaephilus surinamensis. After 24 hours the test was evaluated.
In the above test the compounds of formula I proved effective against Periplaneta americana, Dermestes frischii, Tribolium confusum and Oryzaephilus surinamensis.

-~a , ~ "

Claims

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

1. A compound of the formula wherein X is hydrogen and Y chlorine or X is chlorine and Y bromine.

2. The compound according to claim 1

3. The compound according to claim 1

4. A process for the preparation of a compound according to claim 1 which comprises reacting, in the presence of an acid binding agent, a halophosphate of the formula with a phenol of the formula or with a phenolate of the formula wherein X and Y have the meanings given in claim 1 and Me is an alkali metal, ammonium or alkylammonium group.

5. A method of pest control against insects and representatives of the order Acarina which comprises applying to the locus of the pests a pesticidal amount of a compound according to any of claims 1 to 3.