DE2853124A1 - INSECTICIDES, ACARICIDES AND OVICIDES - Google Patents

Description

ηηηι LQZ JI

ÜSTAV AGROCHEMICKEJ TECHNOLOGY
Br atis I a va- Fr edme sfei e,
CSSR

Insecticides, Acaricides, and Oviaids

The invention relates to insecticides, acaricides and ovicides based on 0,0-dialkyl-S-chloromethyldithiophosphates, in particular to protect agricultural crops against those living in the ground Pests are suitable.

Because of the constantly growing importance and expansion the production of agricultural products gains the protection of cultivated plants against those living in the ground Pests are becoming more and more important. Until recently, soil insecticides were used for this purpose based on compounds from the group of chlorine-containing insecticides such as DDT, lindane, chlordane, heptachlor, Dieldrin et al. Are used. These means have proven themselves to eradicate groups of insects such as Coleoptera,

233- (S9435) -SF-Bk

Lepidoptera and Diptera in postembryonic stages of development are very good, but there is a considerable one The disadvantage of these agents is that they are very difficult to biodegrade and therefore accumulate in the soil and get into the food cycle together with the plant substances. Another questionable one The problem associated with the use of chlorine-containing insecticides is that their long-term or repeated use some pests become immune to it, so that the dosage of such Means per unit area often has to be increased excessively.

For these reasons, various organophosphoric acid ester-based agents have recently been used for such purposes used. For example, it is known to use agents based on O, O-diethyl-O- (4-nitrophenyl) thiophosphate (Parathion), O, O-diethyl O- (2-isopropyl-6-methylpyridin-4-yl) thiophosphate (Diazinon), OjO-diethyl-O-Q-Cmethylsulfiny 1) -phenyl] -thiophosphate (Fensulfotion), 0-ethyl-0- (2,4,5-trichlorophenyl) -ethylthiophosphonate (Trichloronate), 0,0-diethyl-S- (ethylthiomethyl-dithiophosphate (Forat) and numerous others Organophosphorus compounds for combating soil pests to protect important crops such as maize, Use sugar beets, potatoes, cereals, cotton, etc.

The use of 0,0-dialkyl-S-chloromethyldithiophosphates as insecticides and processes for their production are known and for example DE-PS 1 925 468, CH-PS 536 070, AU-PS 432 101 and see U.S. Patent 3,896,219.

909624/0844

However, none of the above patent specifications make any reference to the use of organophosphorus compounds, in which two different alky groups with Oxygen bound, as insecticides, in particular as a means of eradicating soil pests, removable.

The invention is based on the plague that to protect crops in particular against im Soil living pests Insecticides, acaricides and ovicides based on 0,0-dialkyl-S-chloromethyldithiophosphates are advantageous. The agents according to the invention which are effective as insecticides, acaricides and ovicides contain a mixture of the following compounds as an active ingredient:

(a) Compounds of formula I.

(D,

RO N. P -
Ii S- GH ₂ - Cl y: S. RO

(b) compounds of formula II

RO

PS - CH ₀ - Cl (II),

R ¹ OS

(c) compounds of formula III

R ¹ O

R ¹ OS

PS- CH ₂ - Cl (III),

-G-

wherein R is a CL- to C ^ -alkyl group and R is a different Cp- to C ^ -alkyl group. The mixture contains 10 to 30% of component (a), 30 to 60 % of component (b) and 10 to 40 % of component (c)

A significant advantage of the agents according to the invention is that they allow properties such as the initial as well as the residual pesticidal effectiveness depending on the circumstances of the individual Modify components in the mixture in a wide range.

Another advantage of the agents according to the invention compared to the previously used insecticide 0,0-diethyl-S-chloromethyldithiophosphate (Dotan, Chlormefos) consists in its significantly lower toxicity towards warm-blooded vertebrates.

The mixtures which represent the active ingredient of the agents according to the invention can, for example, so be prepared that first a starting mixture of 0,0-dialkyldithiophosphoric acids by reaction with a mixture of aliphatic alcohols with phosphorus pentasulfide is prepared, the molar ratio of Alcohols are chosen differently from one another and the molar ratio of the alcohol mixtures to phosphorus pentasulfide about 8: 1 (see U.S. Patent 2,983,644) target. The mixture obtained in this way is after conversion into the salt form with the corresponding chlorobromomethane implemented in a manner known per se. In this way, they are made more technical and practical Very advantageous compositions of mixtures of 0,0-dialkyl-S-chloromethyldithiophosphates achievable, which is achieved through a completely unexpected,

surprising effectiveness against insects of the groups Coleoptera, Lepidoptera and Diptera in postembryonic Marking stages of development.

The mixtures according to the invention of the active organophosphorus compounds can be in the form of emulsifiable Concentrates, dusting concentrates, dusting or spraying agents, wettable powders, hydrophilic Pollinators, granulated preparations or the like. getting produced. Since they are also technically pure If they are in a liquid state, they can be used in particularly low volume doses and in the form of microcapsules be applied.

The following exemplary embodiments explain the biological effectiveness of the agents according to the invention, whereby the information is not restrictive.

Mixtures according to the invention were used to investigate the insecticidal, acaricidal and ovicidal effectiveness used, their composition and toxicity to warm-blooded vertebrates from the following Table 1 shows.

90982A / 08U

TABEL

Composition of the mixtures and acute oral toxicity to male Wistar rats

mixture RR ¹ P r 0 ζ
A. e η ta
B. η part
C. (mg / rg) I. CpHc C-i Η » 24.5 48.5 ie, 6 36.0 II C ₂ H ₅ 1-C ₄ H ₉ 27.4 57.5 14.5 145.0 III C ₂ H ₅ 1-C ₃ H ₇ 24.0 51.0 23.0 42.0 IV 12.8 43.7 27.5 20.0 V CH ₃ C ₃ H ₇ 15.2 33.6 29.5 190.0 VI CH ₃ 1-C ₄ H ₉ 19.6 42.7 32, B. 340.0 VII part TJ 16.7 32.1 29.1 92.0 VIII 21.7 51.7 25.7 84.0 IX ^C 3 ^H 7 ^{X C} 4 ^H 9 27.2 50.5 21, ε 160.0 X 1-C ₃ H ₇ LC ₄ H ₉ Ζ9.Ϊ. 52.0 Eat, 3 305.0 XI η 11 A —Ρ It
G ₂ H ₅ 1 C ₄ Ii ₉ 18.3 42.3 39.4 160.0

Comparison material Chlormefos standard O, O-diethyl-S-chloromethyldithiophosphate C ₃ H ₅ C ₃ H ₅ 10O ₃ O 7.0

909824/084!

Example 1 - Determination of the acaricidal effect on females of Tetranychus urticae Koch

Working method:

Leaves of bean plants were placed in Erlenmeyer flasks with tap water. On each sheet was with a non-drying adhesive a square

See an area of 2.5x2.5 cm delimited into which 30 breeding females per square were transferred with a fine brush. The leaves were then treated by immersion in previously prepared solutions of the agents according to the invention, the concentrations of which were graded in a geometric series (1,2). After the treatment, the plants were stored in an air-conditioned room (24 ⁰ G; 60-90 % relative humidity). The females on untreated leaves served as controls. The conventional agents Karbofention and Akarition were used for comparison. The test results are shown in Tables 2 and 3 below.

Example 2 - Determination of the acaricidal-ovicidal effect on eggs of Tetranychus urticae

Working method:

Filter paper disks (0.9 cm) were placed on a circular base made of PVC and saturated with water. A bean leaf with a delimited square (2.5 × 2.5 cm.) Was placed on each of the paper. 12 to 15 females were transferred to each square, after which the leaves were stored in an air-conditioned room (24-1 C; 60-90% relative humidity). After 24 hours, the individuals were collected from the squares. The eggs were sprayed with the previously prepared treatment solution using a nebulizer. The concentrations were

0.09824 / 0844

again graded in a geometric series (1,2), where the volume per two leaves was 2 ml. The number of eggs per leaf was determined with a stereo microscope. The treated samples were again stored in the air-conditioned room, where they were incubated for 7 to 9 days became. The pilter paper scrubs applied to the bean leaf with the treating agent became steady kept moist. Untreated eggs served as controls. The conventional means were used for comparison Karbofention or Akarition used. The test results are listed in Table 2.

Example 3 - Determination of the aphicidal contact effect on Aphis fabae (immersion method)

Working method:

In cylinders of 4 cm 0, the lower end faces with Gauze were provided, 33 lice of a homogeneous population were used, whereupon the cylinders with Petri dishes were covered. The treatment agent in those graded according to Examples 1 and 2 above Concentrations were applied by immersing the insect individuals (3 times 3 s). After treatment the lice were dried on the filter paper. Thereafter, the cylinders with the lice were placed in Petri dishes placed, each containing a filter paper disc. Untreated individuals served as controls. Malation Standard was used for comparison. the Test results are also shown in Table 2.

I. Active ingredient 1000 TABEL 2 3 m k e i t (ppm) 5000 .fabae T.urticae TABEL 100 W i r k s a (Eggs) 100 1000 T.urticae A (*) Concentration II 500 (Female) 100 Mixture ^of 1000 {%) 100 - 5000 100 100 _— 100 100 III 500 100 1000 72 5000 100 100 ——— 100 Comparative material: 500 100 mm - - _ - _ Akarition standard 1000 - - - 82 5000 100 100 100 100 0, O-diethyl-S- (4-chloro-500 phenylthiomethyl) di 100 thiophosphate 100 Malation standard 100 0, O-dimethyl-S- (1,2- 100 100 dicarbethoxy) -ethyl- 100 dithiophosphate

Comparison of the acaricidal effectiveness of the individual components with a mixture according to the invention

τη Index of Toxicity ^ ^ ^υ 50 based on Chlormefos

Il 0.0019 163.0

Comparative material:

Chlormefos standard

0, O-diethyl-S-chloromethyl

dithiophosphate 0.0031 100.0

0,0-diisobutyl-S-chloro-

methyl dithiophosphate 0.15 2.0

O-ethyl-0-isobutyl-S-

chlormethyldxthiophosphat 0.013 23 8

909824 / 08U

Example 4

The effect of the agents according to the invention on wireworms (Click beetle larvae; Elateridae) was examined as follows :

The soil used for the experiment was first dried, sieved and processed into the required structure. The earth mass prepared in this way was then weighed out in quantities of 200 g per concentration level. The amount of soil was poured into a 2 l powder jar together with the precisely weighed amount of the preparation, which was then plugged in and worked with a mechanical stirrer for 5 minutes. The test substrate prepared in this way was then filled into cylinders 12 cm in height and 5 cm in diameter, the interior of which was stiffened with Igelit foil; the lower part of the film was fastened with a polyamide fabric and held in place with a rubber band. The cylinder was then placed tissue side down on a petri dish. 5 wireworms were placed in each cylinder and 10 ml of water were poured over them. In order to avoid cannibalism among the individuals, 3 kernels of corn were placed in each cylinder. The cylinders were then stored in an air-conditioned room of 22 * 2 ^° C. and corresponding relative humidity. The experiment was repeated 6 times at each concentration level. Every two days, 10 ml of water was added to each cylinder. After 14 days, an evaluation was carried out in such a way that the dead individuals were counted in each case. Finally, the average percent mortality based on the dead individuals was calculated from three replicates.

The remanent residual effect after 14 days was in

Θ09824 / 0844

determined in the same way with the difference that the wireworms were not added to the substrate until 14 days after the start of the experiment, ie the mixing of the soil with the preparation and filling into the cylinder. The tests were again evaluated after 14 days. The results are shown in Tables 4, 5, 6, 7, 8 and 9. _: -

TABLE 4

Active ingredient
(ppm) At first rest - 12 effect effect concentration 6th 100 100 Mixture of 3 93 100 I - 1.5 93 100 12th 73 86 6th 100 100 3 100 100 II 1.5 80 90 14th 60 12th 6th 100 100 Comparative material: 3 73 100 Pyridation standard 1.5 73 100 O-ethyl-O-isopropy1-0- 33 53 (5 ~ niethoxy-l-methyl-6- Table 5 oxo-1H-pyridazin-4-yl) - thiophosphate

Insecticidal effectiveness of a 0, Ö012- # igen dose of active ingredient, determined under laboratory conditions. Exposure time: 7 days

00982-4 / 0

Mixed mortality (?)

XI 100

Comparison material: pyridation standard O-ethyl-O-isopropyl-0- (5-methoxyl-methyl-6-oxo-1H-pyridazin-4-yl) thiophosphate

100

Control 0

TABEL

Insecticidal effectiveness against wireworms after soil treatment

Active ingredient Biological effectiveness mixture lot 14 days 28 days (kg / ha) (?) (?) XI 1 63.3 56.6 1.5 96.6 86.6 2 100 100 2.5 100 100 3 100 100

Comparison material ': Dursban ~ 5G ~ chlorpyrifos standard

O, O-diethyl-O, 3,5,6-tri- 2,86.6 93.3 chloro-2-pyridyIthiopho sphat

Dyfonate-lOG-fonofos standard O-ethyl-S-phenylethyldithio-

phosphonate 3 93.3 100

Furadan SG carbofuran standard 2,3-dihydro-2,2-dimethylben-

zofuran-7-ylmethyl carbamate 2 100 96.6

Dotan 5G chlormefos standard 0,0-diethyl-S-chloromethyl-

dithiophosphate 2 100 100

Vydate-LOG-oxamyl-Standard 1-Dimethylcarbamoy1-1-methylthiomethyleneamino-

methyl carbamate 3 100 100

carried out in Malinovo, May 1978 909824/0844

Continuation of table 6

Disyston 5G disulfoton standard

0,0-diethyl-S-ethylthioethyldithlophosphate 2 96.6 100

Control (untreated) - 0 0

TABLE 7

Residual effectiveness against wireworms after soil treatment

lung®

Active ingredient Biologically effective ) 28 days 42 days mixture lot speed (%] 93.3 96.6 (kg / ha) lh days 96.6 83.3 XI 1 82.5 100 100 1.5 83.3 100 100 2 100 100 100 2.5 93.3 3 100

Comparative material:
Dursban 5G chlorpyrifos standard

O, O-diethyl-O-3,5,6-trichloro-2-pyridyl thiophosphate 2 76.3 86.3 50

Dyfonate-lOG-fonofos standard

O-ethyl-S-phenylethyldithio-

phosphonate 3 100 96.6 98.7

Furadan-5G-carbofuran standard

2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethyl carbamate 2 100 100 100

Dotan 5G chlormefos standard

0, O-diethyl-S-chloromethyl-

dithiophosphate 2 96.6 100 100

Vydate LOG oxamyl standard

1-dimethylcarbamoyl-l-methyl-

thiomethyleneaminomethylcar-

bamat 3 100 100 86

Disyston 5G disulfoton standard
0,0-diethyl-S-ethylthio-

ethyl dithiophosphate 2 100 ^ 96.6 86.6

Control (untreated) - Q 0 0

® carried out in Malinovo, April 1978

909824/0844

TABLE 8

Remaining effectiveness against wireworms after soil treatment

Active ingredient Biological We mixture quantity {%)

(kg / ha) 14 days 28 days

XI

1 30th 6th 66 6th 1j5 56, 6th 66 6th 2 66 6th 93, 3 2.5 96, 100 3 100 100

Comparative material:
Dursban 5G chlorpyrifos standard

0, O-diethy1-0-3.5 , 6-trichloro-2-pyridylthiophosphate 2 56.6 96.6

Dyfonate-lOG-fonofos standard

O-ethyl-S-phenylethyldithio-

phosphonate 3 100 100

Furadan 5G carbofuran standard
2,3 ~ Dihydro-2,3-dimethylbenzofuran-7-ylmethyl carbamate 2 93 100

Dotan 5G chlormefοs standard
0, O-diethyl-S-chloromethyldithiophosphate 2 100 100

Vydate LOG oxamyl standard

1-dimethylcarbamoyl-l-methyl-

thiomethyleneaminomethylcar-

bamat 3 93.3 100

Disyston 5G disulfoton standard
0,0-Dxäthyl-S-ethylthioethyldithiophosphate 2 93.3 96.6

Control (untreated) - 0 0

® carried out in Vlcany

909824/08 ^ 4

TABLE 9

Initial effect: on wireworms, expressed as a percentage Mortality exposure time: 3 days

0 concentration O = of Active ingredient (%) mixture , 0012 O, 0003 0.0001 XI 87 , 0006 23 13 50

Comparative material:

Chlormefos standard

0,0-diethyl-S-chloro- -. ■

methyldithiophosphate 93 73 57 33

control

Example 5 - Determination of the biological effectiveness of the

mixtures of organophosphorus compounds according to the invention against pests living in the ground,

The procedure was as follows:

The compounds were in the form of a spray, Dotan standard as 5 ^ iges and pyridation standard as 10 # granules applied.

From the dried and sifted earth mass became Trituration preparations based on the compounds according to the invention or the preparations based on organophosphorus compounds used to combat soil pests prepared so that the desired final concentrations of the active ingredients in the soil. 50 g doses of the produced soil samples containing active ingredient were weighed out and placed in Petri dishes filled »whereupon in each bowl after 7, 21 or 35 days

& 09824/084 *

4 ml of water were poured in and 20 four-day-old larvae of Musca domestica L »were placed. The dishes were then brought together with the soil and the larvae in a room of 24 to 26 ⁰ C, whereupon the developed flies were counted after 14 days. The results obtained are listed in Tables 10, 11, the effectiveness of the applied preparations is given as the average percent mortality of the larvae.

TABLE 10

_n . , Amount of active substance Average ^mixture (ppm) Mortality (Ji)

II

III

IV

VI

24 70 12th 36 6th 20th 24 73 12th 56 6th 40 24 93 12th 90 6th 60 24 93 12th 80 6th 26th 24 76 12th 53 6th 10 24 100 12th 86 6th 73 24 76 12th 46 6th 36 24 76 12th 46 6th 30th

Comparative material:
Chlormefο s standard
0,0-diethyl-S-chloromethyl-12
dithiophosphate

Pyridation standard
O-ethyl-0-isopropyl-O- (5-methoxy-1-methyl-6-oxolH-pyridazin-4-yl) thiophosphate

909824/0844

TABEL

Effect of the mixtures according to the invention on fly larvae in the soil, determined under laboratory conditions and given as percentage mortality

Concentration effect after

Mixture of the effective 7 days 21 days 35 days substance (%) {%)

C.CC1.0
C, COOS 66 73 - O, COlO
O ₁ C006 53 IOC
lcü 100
90 O, ν CIG
U, üC06 96
66 ICO - Ü, CClü
c, oüce 50 100
ICO - O, C) OlO
0.0006 ICO
100 100
loo O ₁ COlO
0.0006 ICC
CO IcO
IOC 96
εο O, CCSLO
O.0006 U ICO
70 --- O ₁ CClC
O, OC06 8 y
60 43 - U ₁ CCLO
O, OwCo U ac C, CClC 46 - ...

909824/0844

Continuation, Table 11

Comparative material: Chlormefos standard 0.0010 0.0-Diethyl-S-chloro-0.0006 methyldithiophosphate

66 56

100

Example 6

The effect of the compounds according to the invention was in a further test on larvae of Tenebrio molitor L. according to the procedure described in Example 4 investigated, but no corn kernels were added to the earth mass. The results are the Tables 12 and 13 can be found.

TABEL

mixture

Amount of active ingredient (ppm)

Initial Effect (Percent Mortality) (?)

II

12th 95 6th 64 3 38.5 1.5 ——— 12th 100 6th 90 3 50 1.5 12.5

Comparative material:

Pyridation standard O-ethyl-0-isopropyl-

0- (5-methoxy-1-methyl-

6-oxo-1H-pyridazin-4-yl) thiophosphate

809824/0844

TABEL

Effect of the mixtures according to the invention on larvae of Tenebrio molitor L. in the soil, determined under laboratory conditions and reported as percent mortality

Active ingredient concentration effect after

Mixture tion (.%) 7 days IH days 21 days

t, 0C03 100
ICC. ICO
73 100
IvjC 0,0005 ICO
l,: 0 IGO
lec - G, COC!>
0.0003 IC-O
Γ6 ico
ICC 0, ΙΪΛ. &
O ₁ 0003 100
IOC I CAj
ICC 0, ^ <: ΐ5
0, G / CÜ3 ICO
S3 100
83 ICO
lüÜ C, 0005
C, 0üC3. IGC
ICC IOC
100 ™ 0.0005 '
C, CC03 100
lco IOC
100 mumum ü, OÖCfc
C, 0003 - - 0.0005
0.0CC3 - 0.01 * 05
0, OCCj 26th 13th

Compare material: 100 100 100 Chlormefos standard 0.0005 100 93 100 0,0-diethyl-S-chloro-0.0003 methyldithiophosphate

909824/0844

Claims (2)

BEETZ-LAMPRE CHT-BE ETZ Steinsdorfstr. 10 D-8000 Munich 22 Telephone (089) 227201 -227244- 29 5910 Telex 522048 - Telegram Allpatent Munich 233-29. PATENT LAWYERS Dipl.-Ing. R. BEETZ sen. Dipl.-Ing. K. LAMPRECHT Dr.-Ing. R. BEETZ jr. LAWYER Dipl.-Phys. Dr. jur. U. HEIDRICH Dr.-Ing. W. TIMPE Dipl.-Ing.J. SIEGFRIED Priv.-Doz. Dipl.-Chem. Dr. rer. nat. W. SCHMITT-FUMIAN Dec. 8, 1978. claim 1. Insecticides, acaricides and ovicides based on 0, O ^ dialkyl-S-chloromethyldithiophosphates ge ken η ζ e i c h η et by a mixture (a) 10 to 30 % of compounds of the formula I. RO. ^ "P - S - CH ₂ - Cl - Cl), ■ RO ^ S (b) 30 to 60 % compounds of the formula II RO. R ¹ O '"S and P-S-CH ₂ -Cl (II) (c) 10 to 40 % of compounds of the formula III (III) R ¹ O PS- CH., - Cl 1 S Η RO S with R = a C 1 -C 4 -alkyl group and R = a C "- bxs group different from R as an active ingredient. 233- (S9435) -SF-Bk 2. A method of combating agricultural pests, characterized in that an effective amount a mixture according to claim 1, optionally together with customary auxiliaries and / or carriers, to the protective agricultural crops is applied or introduced into the soil. 009824/0864