DE1813696C3 - Use of phosphorus, phosphonic or thionophosphorus (phosphonic) acid esters for combating rodents and rabbits - Google Patents

Description

CH ₂ -N

R ³

R ⁴

in which R ¹ denotes aryl or alkyl radicals, R ^{2 represents} OR ¹ , aryl or lower alkyl groups, R ³ and R ^{+ represent} alkyl or alkenyl radicals, R ³ and R ⁴ together with the nitrogen atom also represent a 5- to Can form 6-membered heterocyclic ring, R ^{5 represents} lower alkyl, alkyl mercapto, sulfoxyl or sulfonyl radicals, also represents the nitro, cyano or carbonamide group and a halogen atom, R ^{6 represents} a halogen atom, a lower alkyl or the Means nitro group. X is an oxygen or sulfur atom and the index η has the value 0, 1 or 2 or their quaternization products with hydrogen halides, alkyl halides or dialkyl sulfates, for combating rodents and rabbits.

The community is also endangered by the fact that the natural enemies of rodents are lethally damaged by ingesting poisoned rodents. The amido (thio) phosphoric acid esters known from German Patent 10 76 437 must also be used in very high application rates. The products also have a significantly lower level of toxicity than for rats and laboratory mice, against which they are primarily intended to act. So z. B. the oral LD ₅₀ of Ν, Ν-dimethylamidophosphoric acid 4,4'-dichlorodiphenyl ester 25 mg / kg rutle, 10 mg / kg mouse and 125 mg / kg field mouse; field mice even survive 250 mg / kg in individual cases. In accordance with this, our own field tests have already shown that even the use of 1000 g of active ingredient per hectare does not guarantee a reliable total eradication of field mice. The rodemicidally active acetamidido (lhio) phosphoric or phosphonic acid esters according to German patent specification 11 96 897 also require an application rate of at least 1000 g of active ingredient per hectare with an LD ₅₀ of 10 mg / kg rat.

It has now been found that phosphorus, phosphonic or thionophosphoric (phosphonic) acid esters of the general structure

The present invention relates to the use of some known phosphorus, phosphonic or thionophosphoric (phosphonic) acid esters as a surface poisoning agent for combating rodents and rabbits.

It is already known that 1,2,3,4,10,10-hexachlorexo - 6,7 - epoxy - 1,4,4a, 5,6,7,8a - octahydro-1,4,5,8-endo, endodimethannaphthalene, chlorinated camphene, amido (thio) phosphoric and acetamidido (thio) phosphoric acid or phosphonic acid esters in the surface poisoning process to combat harmful Can use rodents. The first two substances mentioned have considerable in practice Gained importance. In many countries, however, the use of 1,2,3,4,10,10-hexachlorexo-6,7-epoxyl, 4,4a, 5,6,7,8,8a-octahydro-1,4,5, 8-endo, endodimethannaphthalene has been banned by law, in Germany it became the official recommendation of the substance withdrawn for the stated purpose because residues with a long-term toxicity when used on the plants treated with it (endangerment of domestic animals and game) as well as in the soil remain behind, so that there is a risk of groundwater poisoning. In addition, the said Substance extremely toxic to fish. In the case of chlorinated camphene, very high application rates have to be used. This active ingredient is also very toxic to fish. Both chlorinated hydrocarbons make the game stand out Have rodenticidal properties and are therefore particularly suitable for combating rodents and rabbit-like in the surface treatment process.

In the above formula, R ¹ denotes aryl, preferably phenyl or alkyl radicals, preferably having 1 to 3 carbon atoms, such as the methyl, ethyl, n- or iso-propyl group. R ² stands for OR ¹ or lower alkyl or aryl radicals, preferably for the methyl, ethyl, n- or iso-propyl group or the phenyl radical. R ³ and R ⁴ represent alkyl or alkenyl radicals with preferably 1 to 4 carbon atoms, such as methyl, ethyl, n- and iso-propyl, allyl. 2-cyanoethyl, n- and iso-butyl radicals, but also higher alkyl radicals, e.g. B. the 2-ethylhexyl radical. In addition, R ³ and R ⁴ , together with the nitrogen atom, can form a 5- to 6-membered heterocyclic ring, preferably the pyrrolidine, piperidine, morpholine or piperazine radical. R ⁵ stands for lower alkyl radicals, preferably methyl, also for the nitro, cyano or carbamido group and for a halogen, preferably

wise chlorine atom. In addition, R ^{5 can} also represent a lower alkyl, preferably methyl mercapto, sulfoxyl or sulfonyl group. R ⁶ represents a halogen, preferably chlorine atom, a lower alkyl, preferably Methvl- or Nitrocriinne, X isl η has an oxygen or sulfur atom, and the index has the value 0, 1, or second

Compounds of formula (I) are obtained in a known manner, for. B. after the sewing of the German

. decription I ?. 11 654 according to the following reaction scheme (11):

(R ⁶ ) "TI + ^CH 2 ° +

R ⁴

OH

-H-, O

X OR ' X OR ' I / II / 0 -P Cl-P \ R ² J _n ZV-CH ₂ - N

(St.

R ⁴

R ⁵

The compounds of the formula (I) can be converted into water-soluble ones by quaternizing the aminomethyl group Bring shape. Suitable quaternizing agents are e.g. B. halogen, especially hydrogen chloride, Alkyl halides, especially iodides and dialkyl sulfates, but preferably dimethyl sulfate.

Some of the substances to be used according to the invention have already been described as insecticides. However, it is extremely surprising that, in contrast to other toxic (thio) phosphoric acid or phosphonic acid esters are fully rodenticidal with very low application rates and moreover not the aforementioned harmful side effects of the listed chlorinated hydrocarbons occupy.

The substances to be used according to the invention are suitable because of their rodenticidal properties as Surface treatment agent for the control of rabbits (Lagomorpha) and rodents (Rodentia), such as squirrel-like (Sciuroidae), pocket rats (Geomyoidae) and mouse-like (Muroidae), to which essentially the common dormouse (Museardinidae) and count the mice (Muridae).

The rabbit-like animals include the Leporidae, such as the wild rabbit (Oryctolagus cuniculus), to the croissant-like z. B. the ground squirrel (Citellus citellus) and the ground squirrel (Citelluslaterialis) and to the pocket rats z. B. the Mountain pocket gopher (Thomomys talpoides).

To the dormouse z. B. the dormouse (Glis glis).

The mice essentially comprise in the group the long-tailed mice (Murinae), the rats (RaUus spec), such as the house rat (Rattus rattus) and the brown rat (Rattus riorvegicus); the house mice (Mus spec), such as Mus muscuius; in the hamster-like group (Cricetinae) the Europ. Hamsters (Cricetus cricetus) and in the group of short-tailed mice (Microtinae) z. B. the field (Microtus arvalis), earth (ivlicrotus agrestis) and great vole (Arvicola terrestris). > In addition to their excellent rodenticidal properties, the agents according to the present invention have also good insecticidal, acaricidal, systematic and nematicidal potency.

The active ingredients according to the invention can be used be converted into the usual formulations, such as solutions, emulsions, suspensions, Powders, pastes and granulates. This is obtained in a known manner, for. B. by stretching the active Substance with solvents and / or carriers, possibly with the use of emulsifying and / or dispersants, * obei z. B. in the case of the use of water, optionally organic sol-ventien can also be used as auxiliary solvents. For this purpose, the auxiliary materials are essentially used in question: solvents, such as optionally chlorinated aromatics, e.g. B. xylene, chlorobenzenes, paraffins, such as petroleum fractions, alcohols, (methanol), amines (ethanolamine) and water; Carriers, such as natural ones and synthetic minerals (e.g. kaolins, chalk, highly dispersed silicic acid); Emulsifier, such as non-organic and anionic emulsifiers (e.g. Polyoxyethylene fatty acid esters, alkyl sulfonates) and dispersants such as lignin. The formulations generally contain between 0.001 and 50 percent by weight of active ingredient, preferably between 0.001 and 20%.

The substances according to the invention or their formulations are used in the customary manner carried out, preferably by spraying and dusting on those inhabited by the pests Surfaces.

example 1

Surface poisoning test
Laboratory animal: field mouse (Microtus arvalis)

In a 5 χ 5 m open-air enclosure enclosed with asbestos-cement panels, the floor of which is even and is densely overgrown with grass about 10 cm long, 80 field mice are released. 24 Hours later, when the animals have settled in and made their burrows, a spray

device an aqueous active ingredient preparation evenly spread over the entire area.

To produce a suitable preparation, the active substance is dissolved in a suitable organic solvent (e.g. xylene), a commercially available non-ionic emulsifier (e.g. based on a benzyl hydroxydiphenyl polyglycol ether) is added to the mixture and the emulsion is diluted with water while stirring continuously, until the desired final concentration is reached. 100 ml of the active ingredient-containing broth are applied per m ^{2 of} grass area and the dead animals are collected from the surface of the earth every day in the following period. The final evaluation is carried out on the 6th day after the spraying by digging out the dwellings and, if necessary, careful screening

(> 5 of the upper soil layers. The test success wire by the number of surviving, given ii percent of the total field mice used pressed 0% survivors means total kill ^

• j

The active ingredients used, the concentrations of broth used, the application rates, the toxic doses applied per unit area and the respective control success can be found in the table below. Column HI shows the extraordinarily high rodenticidal potency of the substances according to the invention, column IV shows that the new compounds offer clear advantages over already known substances, also taking into account their peroral acute toxicities. The numbers in column IV indicate how often the dose that is lethal for 1 kg rat in the pro! m ² each applied amount of active ingredient is included. The larger this figure, the less favorable the respective preparation is to be assessed.

Table 1
Area poisoning test field mouse

Active ingredient

1. l, 2,3,4, 10,10-hexachloro-exo-6,7-epoxy-

1. ^ A ^ oJÄSa-octahydro-1,4,5,8-cndo, -cndodimcthannaphthalin (known)

1 a) the same.

2. Chlorinated camphene (known)

ο o- < V-ci

H ₅ Q,

3. N - P
/

H ₅ C ₂ O-

(based on German patent specification 10 76 437) HN S O

\ II /

4. C-NH-P

(known from German patent specification 11 96 897)

5. 0,0-Diethyl-0- (4-nitrophenyl) -thionophosphoric acid ester (known)

6. Untreated control

S OCH ₅

7. H ₃ CS- ^ V- O ■ P

C ₂ H ₅

CH ₂ • N (C ₂ H ₅ J ₂

8. H ₁ CSO

SO ■ C ₂ H ₅

II /
ρ

OC ₂ H ₅ CH ₂ N (C ₂ H ₅ J ₂

Active ingredient conc. Application rate Application rate% survivors

active ingredient in the broth (mg / ™ ² ) after 6 1 days

per hectare LD ₅₀ rat

_(% , (Grams) ^{(mg / kg)}

111 IV V

100

50 2000

1000

1000

200

20th

1.37 *)

0.7 *) 1.6 *)

2.5 **)

10 **)

0.9 **)

0.5 *

! 3.8 0

3.8

3.1 **) 77.5

H) O

*) LDjo value according to DT-PS 12 18 460, column 6. *) LD ₅₀ values determined in the Inst. F. Toxiko! .. Wuppertal.

Example 2

Fish toxicity test

Laboratory animal: goldfish (Carassius auralus)

The method described in more detail in Example 1 is used to produce a suitable preparation of the active compound applied. The experiments take place in 151 full glass aquariums, each with 10 gold

fish with a body length of approx. 5 cm. The aquariums are ventilated during the trial period in the usual way. Feeding with commercially available dry food begins 24 hours after it has been set up of attempts. The water temperature is 24 ° C.

The active substances tested, the concentrations used and the results obtained (LD ₅₀ = concentration at which 50% of the test fish used die) are shown in Table 2 below:

Table 2
Fish toxicity / goldfish

Active ingredient 2. H, CSO - / ~
C. OC ₂ H ₅
.-H ₂ -N (C ₂ H ₅ J ₂ WirkstolT-
conu.
(ppm) % Kill
24 after hours
48 96 0 LC ₅₀
Door 96 hours
(ppm) 1. 1,2,3,4,10,10-HcXaChIOr-CXO-OJ-CpOXy-
l, 4,4a, 5,6,7,8,8a-octahydro-l, 4,5,8-cndo. ") After 1 hour. 0.02
0.01 100 ")
0 0 50 0.01 cndodimethannaphthalene (known) 0.001 0 0 0 SO · C ₂ H ₅ 5
1 100 ")
0 0 between
I and 5

Substance 2 is at least 100 times less toxic to fish than substance 1.

From the literature (Effects of Pesticides on Fish and Wildlife, US Fish and Wildlife Service Circular 226, Aug. 1965, p. 56), the result of a finding made on young forest with chlorinated camphene is quoted for comparison: At 65 ° F (18, 3 ° C) the LC ₅₀ (96 hours) is 0.0018 ppm.

Example 3
Basic toxicity test / Greifvögcl

Test animals: 2 Waldkiiuzc (Slrix aluco)
1 rough-footed owl (Acgolius tcngmalmi)

The individual owls kept in wire cages received 5 field mice on each of 10 days under practical conditions (as described in example 1) with an intentionally excessive application rate of 150 grams of active ingredient No. 8 (see Table 1) per hectare had been killed. The two Waldkiiuzc ate a total of 17 and 25 respectively, the rough-footed owl 26 ate field mice. None of the owls showed symptoms of intoxication during the feeding period and the 2-week follow-up period.

On the other hand, from a work by II Sch m i d t and G. Wc 11 e η s t e i η (AIIg. Forstzcitschr., 13th year, No. 22 [1958], pp. 301 to 305) that birds of prey die when they eat field mice with the active substances identified in Table 1 with nos. 1 and 2 have been killed.

Example 4

Secondary toxicity test / Carnivorcn
. »5 Test animal: house cat (Felis domesticus)

3 house cats kept individually received 4 field mice each on 4 consecutive days, which as in Example 3 detailed, with an overdose of 150 grams of active ingredient per hectare under practical conditions had been killed. Each tomcat ate all 16 poisoned mice. During the trial period and the 2-week follow-up, no animal showed any impairment of its well-being.

Example 5

Determination of residues on the green plant and in the soil

For the production of a suitable active ingredient preparation proceed as described in more detail in Example 1 and prepare a 0.01 percent by weight active Aqueous emulsion containing substance. With this ('S broth a 4 χ 4m large lawn (grass height approx. 10 cm) evenly sprayed. The treatment mentioned corresponds to the increased amount of active ingredient applied to fight the big voles.

709 Θ42 / Β1

Immediately after the spraying as well as in the following period, representative grass and soil samples are taken taken and analyzed for their active ingredient residues. The findings obtained are in the following Table 3 compiled. It can be clearly seen that the active ingredients to be used according to the invention with regard to the toxic residues on grass and earth are to be assessed considerably more favorably than the state-of-the-art

10

equivalency. The values given for 1,2,3,4,10,10 - hexachlorexo - 6,7 - epoxy - 1,44a, 5,6,7-8,8a - octahydro -1,4,5,8 - endo, endodimethannaphthalin are a work by J. Hurt er, H. Zu rrer and E. Re u thinger (Z. f. Lebensmittel-Unters.- und -Forschg., 130 [1966], pp. 20 to 25) and relate to the usual application rate for this active ingredient to control the great vole of 400 grams of active ingredient per hectare

Table 3

Active ingredient residues on the green plant and in the soil

Active ingredient

On residues (ppm) wall on grass after weeks ge

in soil (layer thickness 15-20 cm)
after weeks

Wst. O 2 4 6 17 24 26 46 48 0 2 4 6 17 26 48

Per

Ha)

1. l ^ AlO.IO-Hcxachlor-exo-o / i-epoxy- 400 χ χ χ χ 1.9 0.163 0.118 0.02 Spu- χ χ χ χ 2.1 χ 0.16 M ^ Sö ^ SaoctahydroIASS _{) bi bj bj b) bi}

a)

^ y
endo, endodimethannaphthalene
(known)

0.420 0.156 0.1 to
a) a) a) a)

SO ■ C ₂ H ₅ 2. HjCSO - ^^ VOP 100 1.6 0.3 nnnn χ χ χ χ χ _η . _η . 0.1 <0.1 η.η. χ χ χ

IO ■ C ₂ H ₅

CH ₂ -N (C ₂ H ₅ I ₂

(Continuation)

Active ingredient residues on the green plant and in the soil

Active ingredient

Residues (ppm)

Wall-

mcn- on grass after weeks in soil

ge

(6

Ws'- 0 2 4 6 17 24 26 46 48 0 2 4

Per

Ha)

in soil (layer thickness 15 20 cm)
after weeks

6 17 26 4S

SC) -C ₁ H,

.1 11., CS <> () ■ 1>

V ₂ U,

CH ₂

a) Ulcralurangubcn (see above).

b) Layer thickness 0.5 cm.

c) RcIaI. Fluctuates; · depending on the bodcnatt. χ = No determination.

n.n. --- Not detectable,

HX) 1.3 0. «O, 4.'il) .2 χ χ " η. χ

n.n. n.n. n.n. n.n. χ ii.n. x

In an analogous way: as described in Example 1, the /.usainirnrnpcsU-llt irksloffc can be used as a poisoning agent.

Table 4

Compounds of general structure (Hl)

(IH)

(Unless otherwise stated, R ^J to R ^{6 represent} hydrogen atoms.)

R ¹ R ² X Λ LrIi) ₂ R ³ R ⁴ R ⁵ R ⁶ LD ₅₀ in mg / kj
Rat per os C ₂ H ₅ QH ₅ S. N (QH ₅ J ₂ CH ₃ ^ 1 C ₂ H ₅ OQH ₅ O N (QH ₅ ) ₂ Cl 1 to 2.5 C ₂ H, OC ₂ H ₅ S. N (QH ₅ ) ₂ Cl ~ 5 QH ₅ QH ₅ S. N (QH ₅ J ₂ Cl 0.2 to 0.5 C ₂ H ₃ OQH ₅ O N (QH ₅ J ₂ Cl Cl ~ 2 QH ₅ OC ₂ H ₅ S. N (C ₂ H ₅ ) ₂ Cl Cl- 7 to 8 QH ₅ C ₂ H ₅ S. N (C ₂ H ₅ J ₂ Cl Cl ~ 2 C ₂ H ₅ OC ₂ H ₅ O N (CH ₃ J ₂ Cl Cl 12 to 25 C ₂ H ₅ OC ₂ H ₅ O N (C ₂ H ₅ J ₂ Cl Cl Cl 2.5 to 5 C ₂ H ₅ OC ₂ H ₅ S. N (QH ₅ J ₂ Cl Cl Cl 4 to 5 QH ₅ C ₂ H ₅ S. N (C ₂ H ₅ y Cl CI Cl 1 to 2 C ₂ H ₅ QH ₅ S. N (CH ₃ J ₂ Cl Cl Cl 1 to 2 C ₂ H ₅ C ₂ H ₅ S. N (CH ₃ J ₂ SCH ₃ ~ 10 C ₂ H ₅ OQH ₅ S. N (C ₂ H ₅ ) J. SCH ₃ ~ 1 C ₂ H ₅ OC ₂ H ₅ O N (CHj-CH = CH ₂ Jj SCH ₃ ~ 10 C ₂ H ₅
C ₂ H ₅ QH ₅
OC ₂ H ₅ S.
S. N (CH ₂ -CH = CH ₂ J ₂
-α SCH ₃
SCH ₃ 25 to 50
~ 7 C ₂ H ₅ C ₂ H ₅ S. ¹ V SCH ₃ C ₂ H ₅ OC ₂ H ₅ S. SCH ₃ - 15 QH ₅ C ₂ Hs S. / "■ \
NO SCH ₃ IO to 25 C ₂ H ₅ OCjH ₅ O SOCH ₃ 20 to 37 C ₂ H ₅ OC ₂ H ₅ S. { C ₂ H ₅ J ₁
N (C ₄ H ₁₁ -Ii) ₂ SOCH ₃ 37 to 75 C ₂ H, C ₂ H ₅ S. N (C ₄ H ₉ -Ii) ₂ SOCH ₃ 25 to 50 QH ₅ OCjII ₅ S. N (C ₄ IL ₁ -Ii) ₂ SOjCH ₃ 2 to 4 QH ₅ OC ₂ H ₅ O N (C ₂ II ₅ J ₂ SO ₂ CH ₃ 0.5 to 1 C ₃ H ₇ -I OC ₃ H ₇ -I O N (C ₂ Ii ₅ J ₂ SO ₂ CH ₃ - 25th C ₂ Hs OC ₂ II ₅ S. N (C ₂ H ₅ J ₂ SOjCH, - 12.5 C ₂ H, c.iu S. N (C ₄ ILrIi) ₂ SO ₂ ClI, 4 to 5 N (C ₄ I

13th

continuation

OQH,

Table 5

Compounds of the general structure (IV) X OR ¹

14th

QH ₅ OC ₂ H ₅ O N (CH ₂ - CH = CH ₂ ) j SO ₂ CH ₃ QH ₅ QH ₅ S. N (CH ₂ -CH-CH ₂ ) J SO ₂ CH ₃ QH ₅ OC ₂ H, S. N (QHs) ₂ CN QH, C ₂ H, S. N (C ₂ H ₅ ), CN QH ₅ OC ₂ H ₅ S. N (CH ₂ -CH = CH ₂ J ₂ CN QH, C ₂ H ₅ S. N (C ₂ Hs) ₂ CONH ₂ QH ₅ OC ₂ H ₅ S. N (C ₂ Hs) ₂ NO ₂ QH, C ₂ H ₅ S. N (QH ₅ J ₂ NO ₂ QH, OC ₂ H ₅ S. N (CH ₂ CH ₂ -CN) ₂ NO ₂ C ₂ H, OQH ₅ 0 N (C ₄ H ₉ -I) ₂ NO ₂ QH, C ₂ H, S. N (QH ₉ -Ii) ₂ NO ₂ QH, OQH ₅ 0 N (CH ₂ -CH = CH ₂ ) J NO ₂

NO ₂

CH ₃

(Unless otherwise stated, R ⁵ to R ^{H are} hydrogen atoms.) IO It ² x K ¹ K "R 'R' ·

C ₂ H, QiI ₅ S

C ₂ II, OC ₂ II ₅ S

C ₂ II,

R- '-I- R ⁴ :

n '

(Ί

R ¹ R ^B

Cl

Cl

LI) _5n in mg / kJ Raltc per os

5 to 10

5 to 10

-2

~ 3

~ 20 to 5C

5 to 10

-0.5

10 to 20

10 to 20

5 to 10

-20

0.5 to 1

C ₂ H ₅ C ₂ H ₅ S. N (CH ₂ -CH-C ₄ H ₉ I ₂ N (C ₂ H,) ₂ NO ₂ CH ₃ ~ 5 C ₂ H ₅ QH ₅ S. QH, N (CH ₂ -CH = CH ₂ ) J NO ₂ CH ₃ -5 N (C ₂ H ₅ ) J. Cl C ₂ H ₅ QH ₅ S. N (C ₂ Hs) ₂ NO ₂ Cl ~ 7 C ₂ H, OC ₂ H ₅ S. N (C ₂ H ₅ ) J. NO ₂ NO ₂ - 10 C ₂ H ₅ C ₂ H ₅ S. NO ₂ 10 to 20 C ₂ H, OC ₂ H ₅ S. NO ₂ 5 to 10 QH, C ₂ H ₅ S. Cl ~ 4

I.Hj .. mg / k υ Rutlc

15th

! ■ ortset / uny

K ¹ K-

R- 'K ⁴ κ ⁵ R "

16

H ¹ R "

LD ₅₀ in

mg.'kg

Rallcpcros

R ⁴ :

C ₂ H ₅ C ₂ H ₅ S

C ₂ H ₅ S

R ¹ HR ⁴ :

SCH,

NO ₂

H)

Claims (1)

Claim: Use of phosphorus, phosphonic or thionophosphorus (phosphonic) acid esters of the form! X OR ¹ I! / O -P