BE807131A - 1,2,4-Thiadiazolyl-(3) (thio) phosphonates and (thio) phosphates - useful as biocides, insecticides and acaricides - Google Patents

Abstract

Cpds. (I) (where R1 is alkyl or alkoxy; R2 is alkoxy, alkylthio, amino, alkylamine, dialkylamino and X is O or S) are prepd. by reacting a cpd. (II) with (III): (where R is H or metal). Thus, (I, X = S, R1 = R2 = OEt) is prepd. from (II, R = H) and ClPS(OEt)2.

Description

       

  "Novel Esters" The present invention relates to phosphates,

  
 <EMI ID = 1.1>

  
Use in the control of parasites. The 1,2,4-thiadiazolyl derivatives correspond to the formula!

  

 <EMI ID = 2.1>


  
in which R represents an alkyl group or an alkoxy group,

  
 <EMI ID = 3.1>

  
amino, an alkylamino group or a dialkylamino group, and X represents an oxygen or sulfur atom.

  
The alkyl, alkoxy, alkylthio, alkylamino and

  
 <EMI ID = 4.1>

  
or branched and their chain contains 1 to 18, in particular, 1 to

  
5 carbon atoms. Among these groups, mention will be made, for example, of methyl, methoxy, methylthio, ethyl, ethoxy, ethylthio, propyl, propoxy, propylthio, isopropyl, n-butyl,

  
 <EMI ID = 5.1>

  
n-pentoxy, n-pentylthio, methylamino, dimethylamino, n-propylamino ot isopropylamino.

  
Preferred due to their action are compounds

  
 <EMI ID = 6.1>

  
R .. represents a methyl, ethyl, methoxy or ethoxy group,

  
 <EMI ID = 7.1>

  
However, particularly preferred are the compounds of formula I in which s

  
 <EMI ID = 8.1>

  
The compounds of formula I can be prepared according to methods known below, for example, as follows:

  

 <EMI ID = 9.1>


  
 <EMI ID = 10.1>

  
As acid-fixing agents, the following bases can be envisaged, for example: tertiary amines such as triethylamine, dimethylaniline, pyridine, or

  
 <EMI ID = 11.1> aromatic carbides such as benzene, toluene, hydro-

  
 <EMI ID = 12.1>

  
esters such as the ethyl ester of acetic acid, ketones such as acetone, methyl ethyl ketone, diethyl ketone, nitriles, for example acetonitrile.

  
Starting materials of formulas II, III and IV are known and can be prepared by known methods.

  
 <EMI ID = 13.1>

  
biocide and, therefore, they can be used to combat various plant and animal pests.

  
They are particularly suitable for combattro

  
 <EMI ID = 14.1>

  
coccidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, PyraJidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Callasipidae family Pulidae, Stomoxydae, Callasipidae, Pulidae Acidae, Callasipidae, Pulidae Acidae, Trasipidae, Pulidae Acidae, Trasipidae, Pulidae Acidae, Trasipidae, Pulidae Iexicidae, Trypidae Acidae, Stomoxidae, Callasipidae Pulidae, Stomoxydae, Callasipidae, Acidae, Stomoxidae, families Trypidae, Stomoxidae, families Tetranychidae, Dermanyssidae.

  
The insecticidal or acaricidal action can be significantly extended by the addition of other insecticides and / or acaricides and it can be adapted to the given conditions. As additives, there may be employed, for example: organic phosphorus compounds, nitrophenola derivatives, formamidines, ureas, carbamates, pyrethrin-like compounds and chlorinated hydrocarbons.

  
The compounds of formula 1 can also be used to combat pathogenic nematodes of plants and partially also to combat representatives of the Thallophyta group such as, for example, pathogenic fungi of plants.

  
The compounds of formula I can be employed alone or with suitable additives and / or carriers. The appropriate carriers and additives can be solid or liquid and they can correspond to the substances usually employed in the art of formulation, for example, natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners. , binding agents. and / or I would go.

  
For the purpose of application, the compounds of formula I can be converted into powdery agents, emulsion concentrates, granules, dispersions, sprays, powder.

  
 <EMI ID = 15.1>

  
sprayer where aqueous preparations are used.

  
 <EMI ID = 16.1>

  
after

  
forms of solid preparations: powdery agents,

  
spreading, granules, coating granules, impregnation granules and homogeneous granules forms of liquid preparations:
a) concentrates of active ingredient dispersible in water:

J

  
spray powders (wettable powders), pastes, emulsions; b) solutions.

  
The content of active material in the agents described above is between 0.1 and 95%; in this case it should be mentioned that when applying from an airplane or by means of other suitable application devices, concentrations of up to 99.5% or even an active ingredient can be used. pure.

  
The active ingredients of formula I can be formulated, for example, as follows:

  
Powder agents: To prepare a powder agent (a) to

  
 <EMI ID = 17.1> a) 5 parts of active ingredient,
95 parts of talc; b) 2 parts of active ingredient, 1 part of highly dispersed silicic acid,
97 parts of talc.

  
The active materials are mixed with the carriers and crushed.

  
 <EMI ID = 18.1>

  
these following:

  
5 parts of active ingredient,

  
0.25 part of epichlorohydrin,

  
0.25 part of cetylpolyglyaiic ether,

  
3.50 parts of polyethylene glycol,

  
 <EMI ID = 19.1>

  
The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then the poly-

  
 <EMI ID = 20.1>

  
under vacuum.

  
Spray powders: To prepare a spray powder

  
 <EMI ID = 21.1>

  
the following constituents:
(a) 40 parts of active ingredient, 5 parts of the sodium salt of lignosulfonic acid,

  
 <EMI ID = 22.1>

  
28.1 parts of kaolin; c) 25 parts of active ingredient, <EMI ID = 23.1>

  
1.7 parts of a Champagne chalk / hydroxyethyl mixture

  
cellulose (1: 1),

  
 <EMI ID = 24.1>

  
46 parts of kaolin; d) 10 parts of active ingredient, <EMI ID = 25.1>

  
saturated fatty alcohols,

  
5 parts of a condensate of naphthalene sulfonic acid / for-

  
maldehyde,

  
82 parts of kaolin.

  
 <EMI ID = 26.1> b) 25 parts of active ingredient, 2.5 parts of epoxidized vegetable oil,

  
 <EMI ID = 27.1>

  
polyglycolic fatty alcohol,

  
5 parts of dimethylformamide,

  
 <EMI ID = 28.1>

  
emulsions can each be prepared having the desired concentration.

  
 <EMI ID = 29.1>

  
94 parts of gasoline (boiling limits: 160 - 190 [deg.] C).

  
 <EMI ID = 30.1>

  
 <EMI ID = 31.1>

  
ve of formula:

  

 <EMI ID = 32.1>


  
in the form of a pale yellow oil with a refractive index

  
 <EMI ID = 33.1>

  
In a way. analogous, the following compounds are also prepared:

  

 <EMI ID = 34.1>
 

  

 <EMI ID = 35.1>

Example 2

  
A) Insecticidal action of ingestion

  
On cotton plants and potato plants, an aqueous emulsion of the active ingredient is sprayed with

  
 <EMI ID = 36.1>

  
After the layer has dried, the plants are infested with

  
 <EMI ID = 37.1>

  
Heliothis virescens and potato plants, with Colorado beetle larvae (Leptinotarsa decemlineata). We perform

  
 <EMI ID = 38.1>

  
In the above test, the compounds according to Example 1 exert a good ingestion insecticidal action against the larvae of Spodoptera, Heliothis and Leptinotarsa decemlineata.

  
 <EMI ID = 39.1>

  
In order to determine the systemic action, root bean plants (Vicia faba) are immersed in an aqueous solution of the active ingredient at 0.01%. (obtained from a concentrate

  
 <EMI ID = 40.1>

  
exert a systemic action on the aphids Aphis fabae.

Example 3

  
Action against Chilo suppressalis

  
Six rice plants of the species "Caloro" are transplanted each time into plastic pots with a larger diameter.

  
 <EMI ID = 41.1>

  
 <EMI ID = 42.1>

  
the insecticidal action takes place 10 days after the addition of the granules.

  
In. the above test, the compounds following the example

  
1 act against Chilo suppressalis.

Example 4

  
Action against soil insects

  
A homogeneous mixture of sterilized compost soil is formed with a spray powder containing 25% of active material, so as to obtain a concentration of 16 or 8, 4, 2, 1 parts per million. In the soil thus treated, we introduce

  
 <EMI ID = 43.1>

  
Pl diatement with 5 larvae of Aulacophora femoralis (age: 15 days /
25 [deg.] C) or 15 eggs of Chortophila brassicae (cabbage flies);

  
on a third corresponding soil sample, we place apple slices as food and 5 Pachnoda larvae

  
 <EMI ID = 44.1>

  
 <EMI ID = 45.1>

  
cutworms (Agrotis Y-L2) is carried out in a similar way,

  
 <EMI ID = 46.1>

  
and 10 parts per million. As food, mallow leaves are used.

  
In the above tests, the compounds according to Example 1 act against the larvae of Aulacophora femoralis, Chortophi: Brassicae, Pachnoda savignyi and Agrotis.

Example 5

  
Tick action <EMI ID = 47.1>

  
There are 5 adult ticks or 50 larvae each time

  
ticks in a small glass tube and immersed for

  
1 to 2 minutes in 2 ml of an aqueous emulsion of a series of dilutions comprising each time 100, 10, 1 or 0.1 parts per million of the test substance. The small tube is closed with a standardized cotton ball and placed on the head so that the emulsion of active material can be absorbed by the cotton wool.

  
For adults, assessment is after 2 weeks and for larvae after 2 days. For each test, two replicates are carried out.

  
 <EMI ID = 48.1>

  
With a series of glue-like dilutions of test A, tests are carried out each time with 20 larvae susceptible or resistant beyond proof (resistance refers to the compatibility of the diazinone).

  
In these tests, the compounds according to Example 1 act against adult larvae of Rhipicephalus bursa and larvae susceptible or resistant beyond evidence of Boophilus microplus.

Example 6

  
 <EMI ID = 49.1>

  
Twelve hours before the acaricidal action test, a piece of leaf is placed on Phaseolus vulgaris plants.

  
 <EMI ID = 50.1>

  
Using a chromatography sprayer, on the stages

  
 <EMI ID = 51.1>

  
Emulsified test so that there is no flow of the spray solution. After :; 2 to 7 days, with a binocular,

  
 <EMI ID = 52.1>

  
ni.-chus urticae.

  
 <EMI ID = 53.1>

  
Action against soil nematodes

  
In order to examine the action of soil nematodes, the active ingredients in each of the concentrations indicated are loaded and intimately mixed in soil infested with nematodes.

  
 <EMI ID = 54.1>

  
In this test, the active ingredients following the example

  
 <EMI ID = 55.1>

  
arenaria.

CLAIMS

  
1. Compounds of formula:

  

 <EMI ID = 56.1>


  
in which :

  
 <EMI ID = 57.1>

  
 <EMI ID = 58.1>

  
X represents an oxygen or sulfur atom.


    

Claims (1)

2. Compounds according to claim 1, characterized in that R. represents a methyl group, an ethyl group, a methoxy group or an ethoxy group, <EMI ID = 59.1> X represents an oxygen or sulfur atom. 3. Compounds according to claim 2, characterized in that R. r represents a methoxy group or an ethoxy group, <EMI ID = 60.1> methylamino or a propylamino group, and X represents an oxygen or sulfur atom. 4. Compound according to claim 2, characterized in that it corresponds to the formula: <EMI ID = 61.1> 5.: A compound according to claim 2, characterized in that it corresponds to the formula: <EMI ID = 62.1> <EMI ID = 63.1> in that it responds to the formula: <EMI ID = 64.1> 7. Compound according to claim 3, characterized in that it corresponds to the formula: <EMI ID = 65.1> 8. Compound according to claim 3, characterized in that it corresponds to the formula: <EMI ID = 66.1> 9. Compound according to claim 3, characterized in that it corresponds to the formula t <EMI ID = 67.1> 10. A process for preparing compounds according to any one of claims 1 to 9, characterized in that a compound is reacted -, formula: <EMI ID = 68.1> with a compound of formula: <EMI ID = 69.1> <EMI ID = 70.1> formula : <EMI ID = 71.1> <EMI ID = 72.1> active, a compound according to any one of the claims 1 to 9, as well as suitable carriers and / or other additives. 12. Use of compounds. according to any one of claims 1 to 9 for combating various animal and plant pests. 13 * Use according to claim 12 for controlling insects and representatives of the order: mites. <EMI ID = 73.1> beat pathogenic nematodes of plants.