AU671840B2 - Methods and agents for combating cockroaches - Google Patents

Description

Our Ref: 481057 P /00/012.

Regulation 3:2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT ft. .ft a. ft.

*.fte ft ft ft. ft ft...

ft...

*4O ft.

ft ft...

ft.

ft.

*e'ft *4 ft...

ft Applicant(s): Bayer Aktiengesellschaft D-51368 Leverkusen

BAYERWERK

GERMANY

DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Address for Service: Invention Title: Methods and agents for combating cockroaches The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 The present invention relates to the novel use of mixtures of certain chemical compounds as substances with pheromone-like action in the combating of cockroaches and to agents for combating cockroaches, containing these mixtures.

Infestation with cockroaches is a considerable hygiene problem on domestic and commercial premises, which in many cases necessitates combating of the cockroaches. Due to their habits, however, cockroaches are difficult to 10 combat. A particular problem here is to attract the cockroaches to mechanical devices for combating them (traps) or to insecticidally active agents. To this end, sex pheromones of female cockroaches have already been employed, but their effectiveness has not always led to satisfactory results. M.E.A. Fuchs, S. Franke and W. Franke (Zeitschrift fur Angewandte Etomologie 99 (1985), 499-503) have found certain carboxylic acids in the excrement of Blattella germanica and have discussed their possible role as part of the aggregation pheromone, 20 but this did not result in any proposals which can be made use of in practice.

It has now been found that the mixtures of at least one compound of the general formula

R

2

O

R3 11 1 (CH)

-C-OR

1

R

4

R

Le A 29 168 1 00 0* in which

R

1 represents hydrogen or C--Cs-alkyl;

R

2 represents hydrogen or Ci-C-alkyl;

R

3 represents hydrogen, hydroxyl or C 1 -Cs-alkoxy; R represents hydrogen, hydroxyl or Ci-Cs-alkoxy;

R

5 represents hydrogen, hydroxyl, amino or Ci-C 5 -alkoxy; and m represents an integer from 0 to or salts thereof, and a) at least one compound of the general formula II 0

II

R) 0

-(CH

2 )n-CH-C -OR 6 9 8 7 in which

R

6 represents hydrogen, C 1 -Cs-alkyl or optionally substituted phenyl;

R

7 represents hydrogen, hydroxyl or Cl-C 5 -alkyl;

R

8 represents hydrogen or C-C 5 -alkyl;

R

9 represents hydrogen or Cl-Cs-alkyl;

R

i o represents hydrogen, carboxyl, C-C-alkoxycarbonyl or optionally substituted phenoxycarbonyl; n represents an integer from 0 to o represents 0 or 1; and p represents an integer from 0 to or salts thereof, and/or b) at least one compound of the general formula III Le A 29 168 2

'Y

0 R 17

R

16

R

15 R14 R 1 3

R

12 0 II I I I I I I II

R

1 8 1

III

in which

R

1 u represents hydrogen, Ci-C 5 -alkyl or optionally substituted phenyl;

R

12 represents hydrogen or C 1

-C

5 -alkyl;

R

13 represents hydrogen or Cl-C 5 -alkyl;

R

14 represents hydrogen or Cl-C-alkyl;

R

15 represents hydrogen or Ci-C-alkyl;

.R

16 represents hydrogen or Ci-Cs-alkyl; 10 R 17 represents hydrogen or C-C-alkyl; represents hydrogen, C 1 -Cs-alkyl or optionally substituted phenyl; q represents an integer from 0 to r represents an integer from 0 to 15 s represents an integer from 0 to 10; and t represents an integer from 0 to or salts thereof, can be employed particularly advantageously in the combating of cockroaches.

20 The expression "compounds of the general formula II" includes the cis and the trans isomers and also mixtures of these isomers.

In the text which follows, the expression "compounds of the general formulae I, II and III" also includes the Le A 29 168 3 salts of those compounds of the formulae I, II and III which carry one or more acid groups and can thus form salts with bases.

The mixtures according to the invention have pheromonelike activities with respect to cockroaches and are suitable for attracting the cockroaches to specific locations and/or prolonging the duration of stay at these locations, where they can be combated using mechanical and/or chemical means. The compounds of the formulae I, II and III are stable and easily accessible via synthesis and are highly active in the mixtures according to the invention.

In the general formulae above and in the definitions of radicals listed below, the radicals have the following 15 general and preferred meanings: Alkyl as such or as a constituent of alkoxy or alkoxycarbonyl denotes straight-chain or branched alkyl having 1 to 5, preferably 1 to 4 and particularly preferably 1 to 3 carbon atoms, with methyl, ethyl, n- and i-propyl, 20 s- and t-butyl being mentioned specifically, in which case methyl and ethyl, especially methyl, should be particularly emphasised.

In optionally substituted phenyl, phenoxy or phenoxycarbonyl, the phenyl ring preferably carries from one to three, particularly preferably one or two substituents, which may be the same or different. All substituents Le A 29 168 4 usual in the active substance chemistry may be present as substituents. Preferred substituents which may be listed are: Ci-C 4 -alkyl, Cl-C 4 -alkoxy, C,-C 4 -alkylthio, C 1

-C

4 halogenoalkyl, Ci-C 4 -halogenoalkoxy, nitro, hydroxyl and halogen (preferably fluorine, chlorine and/or bromine).

The compounds of the general formulae I, II and III which carry one or more acid groups (especially carboxyl groups) can also be present as salts with bases. The salts can be formed with inorganic bases, such as alkali metal and alkaline earth metal bases (preferably with the hydroxides, carbonates or hydrocarbonates of sodium, potassium or calcium) or preferably with organic bases, (especially Cl-C 4 -trialkylamines optionally substituted by HO groups). The compounds of the general formulae I, II 15 and III are preferably employed in the form of the free acids.

R

1 represents in the general formula I preferably hydrogen or Ci-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly 20 preferably hydrogen.

9

R

2 represents in the general formula I preferably hydrogen or Cl-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly preferably hydrogen.

R

3 represents in the general formula I preferably hydrogen, hydroxyl or C 1

-C

3 -alkoxy, particularly Le A 29 168 5 preferably hydrogen, hydroxyl, methoxy or ethoxy and very particularly preferably hydrogen or hydroxyl.

R

4 represents in the general formula I preferably hydrogen, hydroxyl or C-C 3 -alkoxy, particularly preferably hydrogen, hydroxyl, methoxy or ethoxy and very particularly preferably hydrogen or hydroxyl.

R

5 represents in the general formula I preferably hydrogen, hydroxyl, amino or Cl-C3-alkoxy, particularly preferably hydrogen, hydroxyl, amino, methoxy, ethoxy and very particularly preferably hydrogen or amino.

m represents in the general formula I an integer, preferably from 0 to 5, particularly preferably from 0 to 3 and very particularly preferably 0, 1 or 2.

15 In the compounds of the general formula I which can be used in accordance with the invention, the radical indicated as preferred, particularly preferred or very ,particularly preferred can also be present in any desired combination with one another.

20 It is preferred according to the invention to use the compounds of the general formula I in which a combination of the definitions listed above as preferred is present.

It is particularly preferred according to the invention to use the compounds of the general, formula I in which a Le A 29 168 combination of the definitions listed above as particularly preferred is present.

It is very particularly preferred according to the invention to use the compounds of the general formula I in which a combination of the definitions listed above as very particularly preferred is present.

Compounds of the formula I which can be used according to the invention and which may be listed, by way of example and with particular emphasis, are specifically the compounds of Table 1, in which the compounds of the formula I/3 to 1/5 should be very particularly emphasised.

Table 3.

Compound R' R 2

R

3

R

4

R

5 m 15 No.

I/1 H H H H H 0 (Benzoic acid) 1. I/2 H H H H H 1 (Phenylacetic acid) S. /3 H H H H 2-NH 2 0 (Anthranilic acid) 1/4 H H 3-OH H H 2 (3-(m-Hydroxyphenyl)-propionic acid) I/5 H H 4-OH H H 2 (3-(p-Hydroxyphenyl)-propionic acid) Le A 29 168 7

R

6 represents in the general formula II preferably hydrogen or C 1

-C

3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly preferably hydrogen.

R

7 represents in the general formula II preferably hydrogen, hydroxyl or C 1

-C

3 -alkyl, particularly preferably hydrogen, hydroxyl or methyl and very particularly preferably hydrogen.

R

8 represents in the general formula II preferably hydrogen or Ci-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly preferably hydrogen or methyl, R represents in the general formula II preferably hydrogen or C-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly preferably hydrogen or methyl.

R

10 represents in the general formula II preferably hydrogen, the carboxyl group (-COOH) or Ci-C3-alkoxycarbonyl, particularly preferably hydrogen or the carboxyl group and very particularly preferably the carboxyl group.

n represents in the general formula II an integer from preferably 0 to 18, particularly preferably from 0 to 16 and very particularly preferably from 1 to 16.

Le A 29 168 8 o represents in the general formula II preferably 0 or I and particularly preferably and very particularly preferably 1.

p represents in the general formula II an integer from preferably 0 to 18, particularly preferably from 0 to 5 and very particularly preferably 0, 1 or 2.

In the compounds of the general formula II which can be used in accordance with the invention, the radicals indicated as preferred, particularly preferred or very particularly preferred can also be present in any desired .*.*.combination with one another.

S.

It is preferred according to the invention to use the compounds of the general formula II in which a combination of the definitions listed above as preferred is a present.

o. It is particularly preferred according to the invention to use the compounds of the general formula II in which a combination of the definitions listed above as particularly preferred is present.

20 It is very particularly preferred according to the invention to use the compounds of the general formula II in which a combination of the definitions listed above as very particularly preferred is present.

Very particularly preferred are those compounds of the Le A 29 168 9 10 formula II in which R R 8 and R 9 represent hydrogen, or in which one of the radicals R 7

R

8 and R" represents methyl.

Compounds of the formula II which can be used according to the invention and may be listed, by way of example and particular emphasis, are specifically the compounds of Table 2.

Table 2 Compound No.

R0 Re R 7 p o n II/1 II/2 II/3

C,

11/4 II/5 II/6 11/7 H H -OH (2-Hydroxypropionic acid) H H H H (Caproic acid) H H H H (Palmitic acid) H H H H (Stearic acid) HOOC- H H H (Glutaric acid) HOOC- H H H (Adipic acid) HOOC- H H H (Pimelic acid) HOOC- H H H (Suberic acid)

C

2

H

5 0 0 0 H 0 1 2 H 1 1 H 1 1 12 H 0 1 0 H 0 1 1 1 0 2 1 1 2 II/8

~,A

A Table 2 continued Compound No.

p o n 11/9 11/10 HOOC- H H H H (Azelaic acid) HOOC- one of the radicals H R -R 9 denotes methyl, the others represent hydrogen (Methylpimelic acid) HOOC- one of the radicals H

R'-R

9 denotes methyl, the others represent hydrogen (Methyladipic acid) 2 1 2 0 1 2 0 1 1 S S

S.

S

S.

S

*5 *SS S

S.

II/11

R

11 represents in the general formula III preferably hydrogen or Ci-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly 20 hydrogen.

R

12 represents in the general formula III preferably hydrogen or Cl-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly hydrogen or methyl.

R

1 represents in the general formula III preferably hydrogen or CI-C 3 -alkyl, particularly preferably Le A 29 168 11 hydrogen, methyl or ethyl and very particularly hydrogen or methyl.

R"4 represents in the general formula III preferably hydrogen or C,-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly hydrogen or methyl.

R

15 represents in the general formula III preferably hydrogen or C 1

-C

3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly hydrogen or methyl.

P. represents in the general formula III preferably hydrogen or Ci-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly hydrogen or methyl.

15 R 17 represents in the general formula III preferably hydrogen or C,-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particulary hydrogen or methyl.

R

18 represents in the general formula III preferably 20 hydrogen or Ci-C 3 -alkyl, particularly preferably hydrogen, methyl or ethyl and very particularly hydrogen or methyl.

q, r, s and t represent in the general formula III independently of one another an integer from Le A 29 168 12 II_ preferably 0 to 8, particularly preferably 0 to and very particularly preferably from 0 to 3.

In the compounds of the general formula III which can be used according to the invention, the radicals indicated as preferred, particularly preferred or very particularly preferred can also be present in any desired combination with one another.

It is preferred according to the invention to use the compounds of the general formula III in which a combination of the definitions listed above as preferred is present.

o 0* It is particularly preferred according to the invention to use the compounds of the general formula III in which a combination of the definitions listed above as particularly preferred is present.

00 It is very particularly preferred according to the invention to use the compounds of the general formula III in which a combination of the definitions listed above as very particularly preferred is present.

20 In the compounds of the general formula III the radicals

R

8 0CO- and R"OCO- are preferably in the trans position.

Compounds of the formula III which can be used according to the invention and which may be listed, by way of example and with particular emphasis, are specifically Le A 29 168 13 the compounds of Table 3.

Table 3 Compound R 8

R

17

R

1 6

R

15

R

14

R

13

R

1 2

R

1 t s r q No.

III/1 H H H H 0 0 0 0 (Fumaric acid) The compounds of the general formulae I, II and III are known or can be obtained by generally conventional 10 processes and methods.

According to the invention, mixtures of one or more of the compounds of the general formula I (preferably Compounds Nos. I/1 to I/5 of Table 1) with one or more compounds of the general formula II (preferably Compounds Nos. II/1 to II/10 of Table 2) and/or with one or more compounds of the general formula III (preferably Compound No. III/1 of Table 3) can be used. In this respect a mixture which is to be especially emphasised is one which S contains all Compounds Nos. I/1 to I/5 and all Compounds Nos. II/1 to II/10 and the Compound No. III/1 consists of a mixture of these compounds.

The compositions of the mixtures according to the invention of the compounds of the formulae I, II and/or III can be varied over broad ranges, without significantly impairing their effectiveness. The mixtures contain the Le A 29 168 14 compounds of the formula I preferably to the extent of to 95, particularly preferably to the extent of 20 to and very particularly preferably to the extent of 30 to parts by weight. The compounds of the formulae II and/or III are contained in the mixtures in preferably to 95, particularly preferably 20 to 80 and very particularly preferably 40 to 70 parts by weight.

In a particularly emphasised embodiment, all the compounds of the formulae I, II and/or III are present in approximately equal parts by weight.

In a very particularly emphasised embodiment of the invention, the mixture of the compounds of the formulae I, II and/or III contains at least the following individual compounds (all data are parts by weight): lactic acid (preferably 0.5 to 5 caproic acid (preferably 0.5 3 benzoic acid (preferably 2 to 20 phenylacetic acid (preferably 5 to 40 fumaric acid (preferably 0.1 to 1 glutaric acid (preferably 0.5 to 8 anthranilic acid (preferably 0.3 to 15 adipic 20 acid (preferably 0.3 to 5 methyladipic acid (preferably 0.3 to 5 pimelic acid (preferably 1 to 20 suberic acid (preferably 0.5 to 10 m-hydroxyphenylpropionic acid (preferably 5 to 50 p-hydroxyphenylpropionic acid (preferably 0.5 to 10 azelaic acid (preferably 0.5 to 10 palmitic acid (preferably 0.3 to 8 and stearic acid (preferably 0.3 to 8 Le A 29 168 15 The mixtures of the compounds of the general formulae I, II and/or III can be employed according to the invention in the combating of cockroaches, that is insects of the order Blattariae, in particular of the family Blattellidae, preferably of the species Blattella germanica or of the family Blattidae, preferably of the species Blatta orientalis and Periplaneta americana, but also against other cockroach species, but very particularly preferably against Blattella germanica.

The mixtures according to the invention affect the behaviour of the cockroaches such that the latter can be me found in greater numbers at, or seek out, those locations which have been treated with the mixtures or which mm contain such mixtures. The mixtures according to the invention thus display pheromone-like actions. This e. action occurs in all motile development stages (larvae, adults) of the cockroaches. The mixtures according to the invention can hence be employed, quite generally, in the combating of cockroaches, independently of the nature of the combating method used. In mechanical combating methods they can be employed, by way of example and m preferably, in cockroach traps or devices which use adhesives, or in biological or chemical combating methods or in a combination of such combating methods. In mechanical 25 devices, the mixtures according to the invention can be applied over the entire area or large areas thereof or to suitable discrete sites, for example by painting, spraying, impregnating, printing on, if appropriate in conjunction with other active agents such as attracting Le A 29 168 16 colours, bait materials or other attractants, synthetic and natural insecticides, etc. In biological or chemical combating methods, the mixtures according to the invention can exist in the form of a mixture with the entomopathogenic organisms viruses or microorganisms) or with the natural or synthetic insecticides, or can be present in sufficient proximity to these organisms or substances. Analogous comments apply to a combination of a plurality of combating methods.

A person skilled in the art will be readily capable of determining the mixtures and application methods and amounts which are favourable for the particular intended use on the basis of simple considerations or simple 0o "experiments.

15 The mixtures according to the invention of the compounds of the general formulae I, II and/or III are preferably incorporated into an insecticide-containing bait or into adhesive traps, or applied in the vicinity of the bait material above it). The mixtures can also exist in e 20 a form in which they are released over a prolonged period (slow-release formulations). For this purpose, they can be incorporated, for example, into polymer material, paraffins, waxes and the like or be present in microencapsulated form. Traps which can be used are the customary devices and bait materials which can be used are customary edibly attracting agents. The mixtures of the compounds of the general formulae I, II and/or are preferably employed in amounts of 0.0001 to 100 mg (very Le A 29 168 17 particularly preferably 0.01 to 20 mg) per bait or trap, for example adhesive trap.

The compounds can also be employed in the form of the customary sprays, if appropriate as a mixture with suitable insecticides. In this case, the customary formulations can be used, and can be applied using the application devices which are conventionally used. It is also possible to formulate the mixtures according to the invention of the compounds of the general formulae I, II and/or III, if appropriate as a mixture with suitable insecticides, to give dusts or granules which can be scattered. The application rates of mixtures of the compounds of the general formulae I, II and/or III are preferably 1 to 500 mg per m 2 and particularly preferably 2 to 200 mg per m. The use of the mixtures according to the invention allows the effectiveness of mechanical devices (such as traps, adhesive tapes) and, in particular, of insecticidal agents as well to be improved considerably. The present invention therefore also relates to mechanical devices for combating cockroaches and to agents which contain a mixture of the compounds of the general formulae I, II and/or III. Preferred mechanical devices and agents are the customary cockroach traps which contain, if appropriate, baits, other attractants 25 or edible substances and/or insecticidal substances, as eq well as agents which have a tacky surface to which the cockroaches adhere, which, if appropriate, contain, in addition to conventional carriers and auxiliaries edible substances and attractants and/or insecticidally active Le A 29 168 18 substances a mixture according to the invention of compounds of the general formulae I, II and/or III. In this case, the mixtures according to the invention can be contained in the tacky surface or they can be present in the immediate vicinity of the latter. In the mechanical devices, it is also possible to employ combinations of traps and agents having a tacky surface.

Also part of the present invention are agents for combating cockroaches, which contain a mixture according to the invention of the compounds of the general formula I, II and/or III and at least one insecticidally active substance, if appropriate in addition to conventional carriers and auxiliaries and/or other additives (such as a..

abaits, colorants, attractants), it being possible for the 15 mixture according to the invention to be mixed with the remaining components or to be present in a separate arrangement. These agents can also contain entomopathogenic viruses or microorganisms which are active against cockroaches, either additionally or instead of the insecticidally active substances.

Substances which can be used as insecticidal substances are all those which are active against cockroaches, because there is no undesirable interaction between the insecticidally acting substances and the mixtures according to the invention.

Insecticidally acting substances can be, for example, included among the insecticidally acting phosphoric acid Le A 29 168 19 I ~yl_ esters, carbamates, natural pyrethrines and synthetic pyrethroides, nitroimino, nitromethylene, cyanoimino or cyanomethylene compounds, pyrrolidine-2,4-dione derivatives, pyrazoline derivatives, azadirachtrins, annonines and/or ryanodines.

The following may be listed as insecticidal substances which are particularly preferred according to the invention: 1) Carbamic acid esters of the formula IV i0R20 10 R 1 9 -O-CO-N IV IV 2 1 in which

R

1 9 represents an optionally substituted carbocyclic or heterocyclic aromatic radical or an optionally substituted oxime radical (the radicals R 19 which are 15 illustrated further below being preferred),

R

20 represents Cl-C 4 -alkyl and

R"

2 represents hydrogen, C 1

-C

4 -alkyl or a radical U, where U represents the radical -CO-R 22 in which Le A 2.9 168 20 R 22 represents halogen, CI-C 4 -alkyl, CI-C-alkoxy, Ca-C 5 alkenoxy, C, -C 5 -a ikinoxy, Cl-C 4 -alkylthio, C-C 4 -alkylamino, di-C 1 -C 4 -al kyl amino, C,-C~alkylhydroxylamino, or represents phenoxy, phenyithic or phenylanino, each ofl which is optionally substituted by halogen, nitro, cyano, trifluoromethyl, Cl-C 4 -alkyl, C 1

-C

4 alkoxy, Cl-C 4 -alkylenedioxy, Cl-C 4 -alkylthio, C 1

-C

4 alkoxy-carbonyl, or represents 2,3-dihydro-2,2dimethyl-7-benzofuranyl or represents the radical

,,R

2 3

-O-N=C

*--R2 .:10 in which >2 R 23 represents hydrogen, C-C 4 -alkyl or di-Cl-C 4 -alkylamino-carbonyl and R 24 represents CI-C 4 -alkyl, CI-C 4 -alkylthio, cycnao-C 1

-C

4 alkylthio, CI-C 4 -alkylthio-CI-C 4 -al.kyl, **15 or both radicals R 23 and R 24 together represent C 2 -Cealkanediyl which is optionally interrupted by oxygen, sulphur, SO or 502, or .:in which U represents the radical 25 in which v represents 1 or 2 and Le A 29 168 21 w represents 0, 1 or 2, where, in the case that v represents 2, w denotes C and R 2 represents C,,C 1 alC-C,-alkeyl, C.,-C-alkinyl or C 3

-C

6 -cycloalkyl, each of which is optionally substituted by halogen, or represents phenyl, benzyl or phenylethyl, each of which is optionally substituted by halogen, cyano, nitro, trifluoromethyl, trifluoroniethoxy, trifluoromethylthio, Cl-C 4 -alkyl or Cl-C 4 -alkoxy, or represents the radical :10 in which >2 S. 1 0 :R 2 represents Cl-C 4 -alkyl, C 3 -C-alkenyl, C 3

-C

5 -alkinyl,

C

3

-C

6 -CYCloalkyl or benzyl and R 27 represents Cl-C 4 -alkyl, C 3

-C

5 -alkenyl, C 3 -c 5 -alkinyl,

.C

3 -CG-CYCloalkyl, benzyl, phenylethyl, halogenocarbonyl, formyl, Cl-C 4 -alkyl-carbonyl, C 1

-C

4 -alkoxycarbonyl, C-C 4 -alkoxyphenoxy-carbonyl,

C

3

-C

5 -alkinoxy-carbonyl, C- 5 -alkenoxycarbonyl, C 1 C-alkylthiocarbonyl, Cl-C 4 -alkyl-amino-carbonyl, C-C 4 -alkylhyroxylamino-carbonylI Cl-C-alkyl-phenoxycarbonyl, di-Cl-C 4 -alkyl-aminocarbonyl, phenyithiocarbonyl, phenoxycarbonyl, 2, 3-dihydro-2 ,2-dimethyl-7benzofuranyloxycarbonyl, or represents phenylsulphenyl, phenylsulphinyl, phenylsuiphonyl or phenyl, each of which is optionally substituted by Le. A -29 16 8 22 halogen, cyano, nitro, trifluoromethyl, C,-Cl 0 -alkyl or C 1 4 -alkoxy, or represents the radical

,R

2 8

-CO-O-N=C

29 in which

R

28 has the definition given above for R 23 and

R

29 has the definition given above for R 24 7R 2 6 where, furthermore, in the radical the -R27 radicals R 2 and R" together represent a hydrocarbon chain which has 3 to 8 carbon atoms and is optionally interrupted by oxygen or sulphur, and in which, further, R 2 10 can also represent the same radical to which the radical o: 25 is attached.

Carbamic acid esters of the formula IV which are very particularly preferred as active substance components are those in which 15 R 19 represents radicals from the series comprising phenyl, naphthyl, 2,3-dihydro-7-benzofuranyl, pyrazolyl or pyrimidinyl, each of which is optionally substituted by Ci-C 4 -alkyl, C-C 4 -alkenyl, C 1 alkoxy, C 1

-C

4 -alkoxy-methyl, Ci-C 4 -alkylthio, C1-C 4 alkylthio-methyl, C-C 4 -alkylamino, di-(Ci-C 4 -alkyl)amino, di-(C 3

-C

4 -alkenyl) -amino, halogen, dioxolanyl, methylenedioxy and/or by the radical -N=CH-N(CH 3 2 or in which Le A 29 168 23 R 1 9 represents an alkylidenamino radical of the formula

IR

3 0 in which -3

R

3 and R 31 have the definition given above for R 2 and R 24 respectively, R 20 represents C 1 4 -alkyl and ~2 1 C a l y p e e a l R represents hydrogen or C,- 4 akl (peeal *.hydrogen).

Examples of the carkbamic acid esters of the formula IV which may be mentioned are the following N-methylcarbamic acid esters: 2-methyl-phenyl N-methyl-carbanate, 2-ethylphenyl N-methyl-carbanate, 2-iso-propyl-phenyl, 2-secbutyl-phenyl, 2-methoxy-phenyl N-methyl-carbamate, 2ethoxy-phenyl N-methyl-carbamate, 2-iso-propoxy-phenyl Nmethyl-carbamate, 4-methyl-phenyl N-methyl-carbamate, 4- 15 ethyl-phenyl N-methyl-carbamate, 4-n-propyl-phenyl Nmethyl-carbamate, 4-methoxy-phenyl N-methyl-carbanate, 4ethoxy-phenyl N-methyl-carbamate, 4-n-propoxy-phenyl N- *methyl-carbamate, 3,4, 5-trimethyl-phenyl, N-methylcarbamate, 3, 5-dimethyl-4-methylthio-phenyl N-methylcarbamate, 3-methyl-4-dimethylamino-phenyl N-methylcarbamate, 2-ethyithiomethyl-phenyl N-methyl-carbamate, 1-naphthyl N-methyl-carbanate, 2, 3-dihdyro-2, 2-dimethyl- 7-benzofuranyl, 2,3-(dimethyl-methylenedioxy) -phenyl N- Le A 29 168 24 methyl-carbamate, 2-(4 ,5-dimeth'{l-1, 3-dioxolan-1-yl) phenyl N-methyi-carbamate, 1-methylthio-ethylideri-ainirio N-mnethyl-carbamat., 2-methIylthio--2-methylpropylidenami-nc N-methyl-carbanate, 1- (2 -cyano- et hylthio) -ethyl ideairiino N-methyl-carbamate and 1-methylthiomethyl-2 ,2-dime-thylpropylidenamino N-methyl-carbanate, 2-iso-propoxy--phenyl N-methyl-ca.rbamate being preferred.

2) Carboxylic acid esters of the formula V

R

3 3 06~R- 32 -CO.0-CH -R 34 10 in which R 3 2 represents an open-chain or cyclic alkyl radical 4.44 which is optionally substituted by halogen, alkyl, cycloalkyl, by alkenyl which is optionally substituted by halogen, alkyl and/or alkoxy, by phenyl or styryl, each of which is optionally substituted by halogen, optionally halogen-substituted radicals from the series comprising alkyl, alkoxy, alkylenedioxy and/or alkylthio, by spirocyclically linked, I tooptionally halogen-substituted cycloalk( en) yl which .:20 is optionally benzo-fused, in which furthermore R 3represents hydrogen, alkyl, halogenoalkyl, 1 nl alkinyl or cyano, and R 3 4 represents an optionally substituted alkyl or aryl Le A 29 168 25 radical or represents a heterocycle, or, together with R 33 and the carbon atom to which both radicals are attached, forms a cyclopentenone ring.

Carboxylic acid esters of the formula V which are very particularly preferred as active substance components are those in which

R

32 represents the radical

/R

3

CH=C

H

3 C CH 3 in which

R

35 represents hydrogen, methyl, fluorine, chlorine or bromine and R represents methyl, fluorine, chlorine, bromine,

C-C

2 -fluoroalkyl or Ci-C 2 -chlorofluoroalkyl, or represents phenyl which is optionally substituted by halogen and/or optionally halogen-substituted radicals from the series comprising C 1

-C

4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -alkylthio and/or C-Cz-alkylenedioxy, or in which both radicals R 35 and R 36 represent Cz-Cs-alkanediyl (alkylene); or in which Le A 29 168 26

R

3 represents the radical -CH-R 7 in which 138

R

R

37 represents phenyl which is optionally substituted by halogen and/or by optionally halogen-substituted radicals from the series comprising Ci-C 4 -alkyl, CI-C4-alkoxy, Ci-C 4 -alkylthio or Ci-C 2 -alkylenedioxy and

R

38 represents isopropyl or cyclopropyl; or in which

R

32 represents methyl or one of the radicals S tS

S

CH

3 Z CH3

H

3 C CH 3

H

3 C

CH

3 in which the dotted lines are intended to denote possible double bonds, and in which Le A 29 168 27 R 32 represents hydrogen, C,-C 4 -alkyl, Cl-C 4 -halogenoalkyl, cyano or ethinyl and R 34 represents the radicals from the series comprising phenyl, furyl or tetrahydrophthalimido, it being possible for these radicals to be substituted by halogen and/or radicals from the series comprising Cl-C 4 -alkyl, C 2

-C

4 -alkenyl, Cl-C 4 -alkoxy, C 2

-C

4 -alkenoxy, Cl-C 4 -alkyithio, Cl-C-alkylenedioxy, phenoxy and/or benzyl, which, in turn, can be substituted by halogen, and R 24 preferably representing tetraf luorophenyl, 3,4-dichlorophenyl, tetrahydrophthalimido or :representing phenoxyphenyl which can be substituted in one or both phenyl rings by halogen (preferably fluorine).

Moreover the naturally occurring pyrethroids (such as pyrethreum) are particularly preferred as carboxylic acid esters of the formula V.

Examples which may be mentioned of carboxylic acid esters of the formula V which are particularly preferred according to the invention are 31 f~ 345,6-tetrahydro-phthalimido-methyl 2 2-dimethyl-3- (2methyl-propen-1-yl) -cyclopropane-carboxylate, 3-phenoxybenzyl 2, 2-dimethyl-3- 2-dichlorovinyl) -cyclopropanecarboxylate, a-cyano-3-plienoxy-benzy] 2, 2-dimethyl-3- 2, 2 -dichliorovinyl) -cyc lopropane-c arboxyl ate, a-cyano-4fluoro-3-phenoxy-benzyl 2, 2-dimethyl-3- 2-dichioro- Le A 29 168 28 I _i~ vinyl)-cyclopropane-carboxylate, 2,3,5,6-tetrafluorobenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate, a-cyano-3-phenoxy-benzyl 2,2-dimethyl-3- (2,2-dibromovinyl)-cyclopropane-carboxylate and a-cyano- 3-phenoxy-benzyl 3-methyl-2-(4-chlorophenyl)-butanoate.

3) Phosphoric acid esters and phosphonic acid esters of the general formula VI

A

l.-A-R 4 0

R

3 -A-P VI

\-R

4 1 S. in which 10 A is identical or different and represents 0 or S and B represents 0, S, -NH- or a direct bond between the central P atom and R 41 and

R

39 and R 40 are identical or different and represent 15 optionally substituted alkyl or aryl,

R

41 represents hydrogen, optionally substituted alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl or an oxime radical or represents the same radical to which it is attached.

Particularly preferred phosphoric acid esters and phosphonic acid esters of the formula VI are those in which Le A 29 168 29

R

3 9 and R 40 are identical or different and represent CI-C 4 alkyl or phenyl,

R

41 represents hydrogen, alkyl which has 1 to 4 carbon atoms and which is optionally substituted by halogen, hydroxyl, cyano, optionally halogen-substituted phenyl, carbamoyl, alkylsulphonyl, alkylsulphinyl, alkylcarbonyl, alkoxy, alkylthio, alkoxycarbonyl, alkylaminocarbonyl, the latter in each case having up to 6 carbon atoms, or represents alkenyl which has up to 4 carbon atoms and which is optionally substituted by halogen-substituted phenyl or C 1

-C

4 alkoxycarbonyl, or represents the radical of the general formula

R

4 2

-N=C

R4 3 in which R 42 and R 43 have the definition given above 15 for R 23 and R 24 respectively, or represent cyano or phenyl, and in which

R'

1 furthermore represents dioxanyl which is substituted by the same radical to which R 40 is attached, or R 4 1 represents the same radical to which it is attached, 20 or R 41 represents phenyl which is optionally substituted by methyl, nitro, cyano, halogen and/or methylthio,

R

41 furthermore particularly preferably representing heteroaromatic radicals such as pyridinyl, Le A 29 168 30 quinolinyl, quinoxalinyl, pyrimidinyl or benzo- 1,2,4-triazinyl, each of which is optionally substituted by Cl-C 4 -alkoxy, C-C-alkylthiomethyl,

C'-C

4 -alkyl and/or halogen.

The following may be mentioned individually: 0,0-dimethyl or 0,0-diethyl 0-(2,2-dichloro- or 2,2-dibromovinyl) phosphate, 0,0-diethyl 0- (4-nitto-phenyl) thionophosphate, 0,0-dimethyl 0- (3-methiyl-4-methylthio-phenyl) thionophosphate, 0 ,0-dimethyl0- (3-methvl-4-nitro-phenyl) thionophosphate, -ethyl S-n-propyl 0-(2,4-dichlorophenyl) thionophosphate, 0-ethyl S-n-propy 0-(4-methylthio-pheriyl) thionophosphate, 0,0-dimethyl S-(4-oxo-1,2,3-benzotriazin.-3-yl-methyl) thionothioiphosphate, 0-methyl 0- (2-iso-propyl-6-methoxy-pyrimidin-4-yl) thionomethanephosphonate, 0,0-diethyl 0- (2-iso-propyl-6-methyl-pyrimidin-4-yl) thionophosphate, 0,0-diethyl 0- (3-chloro-4-methyl-cumarin-7I-yl) thionophosphate, 0, 0-dixnethyl 2,2, 2-tricloro-1-hydroxy-ethane-phosphonate, 0,0-dimethyl S--(methylaminocarbonyl-methyl) thionophosphonate.

0-methyl 0- (6-methoxy-2-tert. -butyl-pyrimidin-4-yl) thionoethane-diphosphonate.

Le A 29 168 31 4) Nitromethylene, nitroimino, cyanoimino or cyanomethylene derivatives of the formula VII R47-V-N-C-R44 (VII) 1 1

Q

R

4 6 in which 5 R 44 represents Cl-C4-alkyl (preferably methyl or ethyl), or represents the group

R

48 in which

-N-R

R

4 represents Ci-C-alkyl (preferably methyl or ethyl) or R4 8 together with R 45 represents an optionally *branched Cz-Cs-alkanediyl chain (preferably -(CHo)2- or 15 and

R

4 represents hydrogen or CI-C4-alkyl (preferably hydrogen);

R

45 represents Cl-C4-alkyl (preferably methyl or Le A 29 168 32 _I _I -IY-ILU~UIWI.L ethyl) or together with R 48 represents an optionally branched Cz-C-alkanediyl chain (preferably -(CH2) 2 or -(CH 2 3

R

46 represents NO 2 or CN;

R

47 represents an optionally substituted (preferably substituted by halogen and/or

C-C

4 -alkyl) heteroaromatic radical (preferably pyridyl radical) (R 47 particularly preferably representing the 2-chloro-pyrid-5-yl group); 10 Q represents or and 0* V represents a direct bond or represents a Ci-C 3 -alkanediyl radical (preferably In the following text, some particularly preferred compounds of the formula VII are listed specifically by way of example: C2H 5

CH

3

CH

3 R R-N NH R 5 -N NH R 0-@N CH 3

N-NO

2 CH-N0 2

N-CN

in which R 50 represents the-cH2 -radical.

Depending on their particular physical and/or chemical properties, the mixtures according to the invention of Le A 29 168 33 compounds of the formulae I, II and/or III and/or the insecticidical substances and the mixtures of the mixtures according to the invention of compounds of the formulae I, II and/or III with the insecticidal substances can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with auxiliaries and/or extenders, that is liquid solvents and/or solid e* carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing 15 agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated 20 aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; as solid carriers there are suitable: for example ground natural minerals, such as Le A 29 168 34 kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and 20 synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants, such as alizarin Le A 29 168 35 dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

When formulated as baits (preferably bait formulations for scattering or solid bait formulations), the formulations can additionally contain further additives which attract the cockroaches and/or encourage them to ingest the insecticidal substances. The attractants and edible substances which can be used are all those preparations which are conventionally used, such as natural or synthetic odoriferous substances, colorants and/or substances which are palatable to the cockroaches, such as products based on cereals or sugar which contain starch, protein and/or sugar.

The formulations preferably contain 0.001 to 95, in particular 0.01 to 70, per cent by weight of mixtures of the compounds of the formulae I, II and/or III.

The formulations of the insecticidal substances contain (if appropriate in addition to the mixtures of the compounds of the formulae I, II and/or III) preferably between 0.1 and 95, in particular 0.5 and 90, per cent by weight of insecticidal substances.

The application of the agents for combating cockroaches is effected in a customary manner adapted to the application form.

Le A 29 168 36 The biological activity of the mixtures according to the invention of the compounds of the formulae I, II and/or III will be illustrated with the aid of the following examples.

Example A Improvement to activity of a bait In a room (2.25 x 4.70 m) in each case a hiding place and a drinking site are located in 2 opposite corners, and in the other corners in each case a piece of rusk. One day 0 after releasing 20 male, 20 female and 20 juvenile cockroaches (Blattella germanica), in each case a bait container with an insecticide-containing edible tablet (insecticidal active substance: 0.5% by weight of ethylchlorpyrifos) is placed against the wall at a 15 distance of 40 cm from the rusk.

On the inside of the bait container lid there is a small plate which is treated 1 hour previously with a mixture according to the invention (dissolved in methanol) or only with methanol (untreated bait).

*e 5.4 0. 20 3 rooms were in each case equipped with treated bait containers and 3 with untreated bait containers.

On the following day, the mortality of the male and female animals is determined.

Le A 29 168 37 Test result from the experiments in which the mixture according to the invention which was employed was a mixture of approximately equal parts (parts by weight) of the Compounds Nos. I/1 to 1/5, II/1 to II/10 and III/l ("Mixture Treatment type mortality after 1 day total population Control (insecticide only) 29 10 Insecticide Mixture A emg) 57 Example B Improvement to activity of a spray Ceramic tiles are sprayed with an aqueous spray formu- 15 lation containing the insecticidal active substance cyfluthrin or cyfluthrin and the Mixture A (cf.

Example so that the application rate of cyfluthrin is 20 mg of active substance per m 2 and the application rate of Mixture A is 4 mg per m 2 20 One in each case of these tiles is placed in the corner of a container (49 x 59 cm, height 29.5 cm) in which there are a drinking site, feed, a hiding place and also, introduced 2 hours before, males and females of Blattella germanica (5 of each). Each experiment consists of 3 replications.

Le A 29 168 38 39 Test result (average of 3 experiments): Treatment type mortality in and 1 day Control (insecticide only) 43 Insecticide Mixture A

NOTE:

The foregoing description is substantially as originally lodged and is retained in this form to preserve the fullness of the initial disclosure. The scope of the invention is as defined in the proposed amended claims immediately below.

e 4:0000 *ooo ooo f 0 f 00of ft ft ftf ft ft0 ft 0t

Claims (6)

1. A mechanical device or means for attracting cockroaches, for combatting said cockroaches, said device or means containing a mixture of benzoic acid, phenylacetic acid, anthranilic acid,

3-(m-hydroxyphenyl)pro-pionic acid, 3-(p-hydroxyphenyl)propionic acid, 2-hydroxypropionic acid, caproic acid, palmitic acid, stearic acid, glutaric acid, adipic acid, pimelic acid, suberic acid," azelaic acid, methylpimelic acid, fumaric acid or salts thereof. 2. A mechanical device or means for attracting cockroaches, for combatting said cockroaches, said device or means containing a mixture of 0.5-5% lactic acid, 0.5-3% caproic acid, 2-20% benzoic acid, 5-40% phenylacetic acid, 0.1-1% fumaric acid, 8% glutaric acid, 0.3-15% anthranilic acid, 0,3-5% adipic acid, 0.3-5% methyladipic acid, 1-20% pimelic acid, 0.5-10% suberic acid, 5-50% m-hydroxyphenylpropionic acid, 0.5-10% p- hydroxyphenylpropionic acid, 0.5-10% azelaic acid, 0.3-8% palmitic acid, 0.3-8% stearic acid (all data are parts by weight) or salts thereof. 3. A device or means according to claim 1 or 2, for attracting and combatting cockroaches, which contain, as attractant, a 25 mixture as set forth in claim 1 or 2 together with biological or chemical cockroach combatting substances. *f

4. An agent for attracting and combatting cockroaches which contains *99* 9 at least one entomopathogenic virus or microorganism, and/or at least one insecticidally active substance; and as an attractant for said cockroaches, a mixture as 2 i .1 P,\\'rl~r~l~c1IW8(.0 H, JIMC -41- set forth in claim 1 or 2. An agent according to claim 4 which additionally contains one or more auxiliaries and/or extenders and/or other additives.

6. An agent for attracting cockroaches, which contains a tacky surface to which the cockroaches adhere and which,in the tacky surface or adjacent thereto, contains a mixture as set forth in any one of claims 1 to 3.

7. A method for attracting cockroaches wherein there is employed a device or means according to claim 1 or 2 or an agent according to claim 6.

8. A method for attracting and combatting cockroaches wherein there is employed a device or means according to claim 3, or an agent according to claim 4 or DATED this 5th day of July, 1996. 9o o a. a.* a o a. a S *a *t. a* roo• o BAYER AKTIENGESELLCHAFT 25 By Its Patent Attorneys DAVIES COLLISON CAVE 'cp~-;p V§ A Methods and agents for combating cockroaches Abstract The present invention relates to the novel use of mixtures of certain chemical compounds as substances with pheromone-like action in the combating of cockroaches and to agents for combating cockroaches, containing these mixtures; details should be taken from the description. e 0* o 0 S e *e C SO Le A 29 168