DE2600800C2 - Methods of combating fungi in the household sector - Google Patents

Description

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The present invention relates to a method for controlling fungi in the household sector with "* i! Fe des." known l - ^ - chlorophertoxyH-imidazolyHl ^^ - dimethyl-butan ^ -ons.

It has already become known that H ^ -ChlorphenoxyVl ^ imidazolylKO-S ^ -dimethylbutan ^ -one is a good one The spectrum of activity against human, animal and phytopathogenic fungi shows and is microbicidal (cf. German Offenlegungsschriften 21 05 490 and 23 25 156).

A use of l- (4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dimethyI-butan-2-one for combating However, there is no mention of mushrooms in the household sector.

In addition, it is already known that 2- [N- (trifluoromethyl) -N- (fluorodichloromethy! Thio) -arnino] -benzoic acid salicyl ester (active ingredient of the commercial ^{product 41} EULAN ASEPT P) is used as a disinfectant in the household sector (cf. German Offenlegungsschrift 19 19 180). However, its effect is not always entirely satisfactory, especially against mold and sprout fungi.

A method for combating fungi in the household sector has now been found, which consists in that one l- (4-chlorophenoxy) -l-imidazoryl- (l) -3,3-dirnethylbutan-2-one of the formula

-C (CHj) ₃

can act on mushrooms or their habitat.

Surprisingly, the l- (4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dimethylbutan-2-one shows exactly against those in the household sector for combating fungal groups have a better effect than those from the extended state of the art known 2-rN- (trifluoromethyl) -N- (fluorodichloromethylthio) -amino] -benzoic acid salicylester, which for some Time is used for antimicrobial finishing and is an active ingredient with the same direction of action. Since the substance that can be used according to the invention has a particularly broad spectrum of activity with a high intensity of action, especially against mold, with favorable physical properties at the same time successful use in the household sector is guaranteed.

From the test results disclosed in DE-OS 23 25 156 (cf. Examples A, B, D, E, F and G) it follows that that the compound which can be used according to the invention as well as the other of the general ones listed there Formula (I) encompassed imidazole derivatives have a fungicidal effect on plants. Leave the data do not recognize that the l- (4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dimethyIbutan-2-one in other! Indications, namely in the control of fungi in the household sector, occupies a special position. Exactly for that reason it is to be considered surprising that the MIC values of this compound are substantially lower than those all other substances of this type (see examples of use). Even of the two components that according to DE-OS 23 25 156 actually tested as substances for the preservation of wood pulp, are in Compared to the l-M-chlorophenoxyJ-l-imidazolyHDO ^ -dimethylbutan ^ -one the four or ten times the amount needed to inhibit the growth of Microsporum canis. The MIC value is at Penicillium commune for the bromine compound, forty times as high as that of the compound which can be used according to the invention. aside from that also exhibits the corresponding phenyl compound in the inhibition of Candida albicans a 40lach higher value than the compound which can be used according to the invention.

The l- (4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dimethyibutan-2-one to be used according to the invention is known (see above German Offenlegungsschriften).

The incorporation of the active ingredient of the formula (I) into materials which in the household sector are attacked by fungi are exposed to inhibits the growth of the fungi; thus the original value of the materials is retained. The compound is non-volatile, insoluble in water, insensitive to light and thermally stable, so that it can be used in such Materials is resistant over long periods of time. Examples of materials used in the household sector by fungal growth are adversely affected are lime paints, emulsion paints, wallpaper, joints in tile walls, Furniture. Leather, synthetic leather, bath mats, shower curtains, textiles, carpeting and tent equipment

26 OO 800

The following classes and species of fungi occur in particular in the household sector:

1. Wood:
Basidiornycetes

Ascomycetes

Fungi imperfecti

in particular Merulius lacrimans, Coniophora puteana, brown rot, soft rot fungi, blue fungus and Molds. These lead to the destruction, change in strength and discoloration of wooden materials

(Furniture).

2. Cellulose and paper: (wallpaper, books) in particular Aspergillus species, Penicillium and other molds, as well as other wood-destroying ones Mushrooms.

3. Textiles and leather:

Molds (Aspergillus, Penicillium, Verticillium etc.)

Mold rot fungi These lead to a decrease in the strength of fibers, leather and discoloration (mold stains on textiles, Red coloring of chrome leather).

4. Paints, glue, bitumen: molds

Blue fungus that lead to discolouration through degradation of the dyes or through their own dye production.

Particularly noteworthy is the high intensity of action of the compound of the formula (I) compared to the Pityrosporum ovale, which counts among the sprouts, compared to molds such as Aspergillus niger, Penicillium commune, Erysiphe graminis and against Fungi imperfecti such as Colletotrichum coffeanum, as well as the sporicide Effect at concentrations of 10 mcg / ml against dermatophyte and Aspergillus spores. The connection shows in vitro a high intensity of action with a primarily fungistatic type of action, i.e. H. she inhibits that Growth of mushrooms; fungicidal effects (fungus killing) can be achieved with 5 to 10 times the minimum inhibitory concentration (so-called »MIC values«) can be achieved.

In addition, the compound to be used according to the invention shows a bactericidal effect.

The active ingredient which can be used according to the invention can be used in unmodified form or with a carrier, e.g. B. dispersed on a finely divided egg. Solid or used as dust. Such mixtures can also be dispersed in water with the aid of a wetting agent and the resulting emulsions can be used as a spray. In other ways of working, the products can be used as active ingredients in solvent solutions, oil-in-water or water-in-oil emulsions. The mixtures can be formulated as concentrals and then diluted with other liquid or solid auxiliaries to produce the final treatment mixture. Good results are obtained in particular when mixtures are used which contain 0.5 to 3% active ingredient.

The various possible applications are evident from the following examples:

Example A-I MIC values in
mcg / ml MIC values of the compound
pathogenic fungal species and 1
1 Groups of mushrooms of formula (1) compared to important ones in the household sector
bacteria 1 Dermatophytes Mushroom species 1 Trichophyton mentagrophytes
rubrum 1
1 verruscosum 1
1
1
1-4 Epidermophyton fioccosum 4th Sprouts Microsporon canis
felineum 1-4 Candida albicans
tropicalis
pseudotropicalis
krusei 0.25-0.5 Torulopsis glabrata 1 Cryptococcus neoformans 1 Hisphasic mushrooms Pityrosporum ovale 2 Histoplasma capsulatum Coccidiodes immitis SDorothrix Schenckii

continuation

Groups of mushrooms Mushroom species MIC values in
mcg / ml MIC values
Micro
sporum
canis in mcg / ml
Candida
albicans Penicillium
commune Itssek- Molds Aspergillus fumigatus
Niger
Penicillium comune
Madurella grisea 2
1
1
1 Asper
gillus
Niger Fungi imperfecti Cercospora musae
Collectotrichum coff. 5
5-10 Basidiorpycetes Hypnochus sasakii 10 (MIC 50) bacteria Staphylococcus aureus
Streptococci 50
100 Example A-2 MIC values of the active ingredient of the formula (I) and similar compounds against fungi that <m Hausha
gate occur: Active ingredient

³⁰ according to the invention

- CH - CO - C (CH ₃ ) ₃

known

10

~ CH-CO-C (CHj) ₃

10

10

100

100

40

26 OO 800

continuation

Active ingredient

Br— / T) V Ο - CH- CO -C (CH,),

\ ■ I

Ο —CH- CO - C (CH)),

O - CH - CO - C (CH ₃ ).

N N

0-CH-CO-C (CH,)

L '

—CH-CO —C (CH ₃ ).,

O - CH - CO - C (CH ₅ ),

N
Ii N

MIIK values in mcg / nil

Cumliüu alhiciins

Microsporum
can is

40

<1

32

40

40

100

Pcnicillium commune

40

> 64

100

<1

100

100

Aspcr-

gillus

Niger

I examples

! Reciprocal germ inhibition values compared to Eulan Asept P, as a handset product with the same direction of action

! preparation

Bact. Slaphj'lo- Saccha- Candida Asper- Asper-

nicsen- coccus romyces albicans gillus ijillus

tcricus aureus spec. terreus iniger

Trichophyton menlagrophyles

Paecilo-

myces

varioti

Penicillium camerunense

VO-CH-CO-C (CHj) ₃

: u — ν

i * Eulan Asept P 30% commercial product 500 18 000 80 000 80 000 18 000 42 000 80 000

000 30 000

000 30,000 <3,000 3,000 30,000

<3

80

30th

I 26 OO 800

■ j "; examples

'; Equipment of shoe midsole materials

•H
K- _L >, test arrangements 5

': l I. Direct contamination test

I A 3 x 3 cm piece of the plastic midsole material next to a blank control

fr! Contains 1.5 percent by weight of active ingredient, was placed in damp chambers, soaked with Nervina malt solution io

% and with approx. 2-3 x 10 ¹ germinable particles or cells of

f ■ Trichophyton mentagrophytes

'' Trichophyton rubrum

i * as prototypes for dermatophytes,

t "Candida albicans,

as the guiding principle for Helen, ">

Aspergillus fumigatus and
Penicillium comune

inoculated as a representative of the mold group. 25th

The material prepared in this way was incubated for 7 days at 28 ° C. and from the 3rd day onwards daily for bacterial growth checked.

2. Agar diffusion test

Pieces of the midsole material approximately 1 x 1 cm in size were placed in Petri dishes and covered with Sabouraud agaf. After the agar had solidified, 1 × 10 ⁵ infectious particles of the fungal species were found

Trichophyton mentagrophytes

Trichophyton rubrum ³⁵

Candida albicans

Aspergillus fumigatus and

pcniciiiium comune

suspended in 0.5 ml of physiological saline solution, split up homogeneously on the Petri dishes and the Petri dishes door incubated for ^{4 days at 28 ° C.}

Results
1. Direct contamination test 45

On the unfinished control material, all germs showed normal growth. The one with l- (4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dimethylbutan-2-one The finished material showed in dermatophytes and Aspergillus as well as Penicillium - compared to the control - about 80% growth inhibition of the Germs, with Candida an approx. 30% inhibition of growth. 5υ

A repetition of the experiment with plastic material that contained 2 to 3% by weight of active ingredient, led to a complete inhibition of growth in all fungi tested.

2. Agar diffusion test

The inhibition zones achieved in the diffusion test are summarized in the following table:

preparation Inhibition zones in mm 0 at Trich. rubr. Asp. Fum. (Active ingredient of formula I) Cand. silly Trich. ment. 0 0 control 0 0 38 35 1.5% active ingredient 38 38 45 38 2% active ingredient 38 46 50 39 3% active ingredient 41 50

Example D Finishing of Lefamaterial (leather fiber)

5 The test is carried out in the contamination test and agar diffusion test in accordance with the test arrangements in the example C.

Composition of the material:

70 parts of leather fiber 30 parts of natural rubber corresponds to 50 parts of 60% Ndiurlatex 1.5 parts Vulkanox NKF (an adhesive)

a) 2 or

b) 3 parts of active ingredient of formula (I)

15 The dermatophytes Trichophyton mentagrophytes and Trichophyton rubrum were tested for Aspergillus fumigatus mold and the yeast Candida albicans.

Result

20 In the contamination CSt as well as in the agar diffusion CSt, he was fully effective.

Example E.

Household spray

I) Agar plates inoculated with germs are treated with spray formulations (according to Example F):

Spray Asp. Asp. Poecilo- Penic. Trich. Candida Staph. Bac.

permanent niger terrens myces camer. ment. albicans aureus mcscni.

Spray 1 sec. Without without without without without without without without

form- fouling fouling fouling fouling fouling fouling fouling

lation I 5 _se c. like. like. like. like. like. like. like.

Spray formulation II

2) the spray formulation III (according to Example F) was tested against the following germ carriers:

Shoe leather

Textile mixed fabric τ, ■ . ,, -τ- · l. j · · _.

Woodchip wallpaper test germs: Aspergillus terreus, Tnchoderma viride

Filter paper 45

2000 mold colonies per germ carrier were used as germination seeds.

Result
50 With spray times of 1 and 2 see. the above-mentioned germ carriers were still without vegetation after 14 days.

Example F Aerosol formulations

Formulation I 0.5% 1- (4-chlorophenoxy) -l-imidazolyl- (1) -3,3-dimethylbutan-2-one 0.1% Evergreen 10 745 H + R *) 39.4% Isopropanol 60.0% Frigen 11/12 (30:70) **)

Formulation II 0.5% M4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dirnethylbutan-2-one 0.1% Evergreen 10 745 H + R *) 39.4% Ethanol 60.0% Frigen 11/12 (30:70) **)

1 see. the same the same the same the same the same the same the same the same 5 sec. the same the same the same the same the same the same so, the same

OO 800

Formulation III

0.5% H4-chlorophenoxy) -1-imidazolyl- (1) -3,3-dimethylbutan-2-one
0.1% Evergreen 10 745 H + R *)
59% isopropanol
39.9% Frigen U / 12 (30: 70) **)

*) Perfume oil as a fragrance component.
**} Frigen 11 = CCl ₃ F;
Frigen 12 = CCl ₂ F ₂ .

Manufacturing example

O-CH-CO-C (CHj) ₃

y- _N

12.25 g (0.05 mol!) Of l-bromo-i- (4-chlorophenoxy) -33-dimethylbutan-2-one and 12 g (0.18 mol) of imidazole are used
after dissolving in 120 ml of acetonitrile, heated to boiling under reflux for 18 hours. After distilling off the
150 ml of water are added to the residue using a solvent in vacuo and the aqueous phase is then removed
treated three times with 30 ml of water each time, dried and the solvent was distilled off in vacuo. To
recrystallization of the residue from approximately 400 ml of ligroin gives 10.5 g (72% of theory) of 1- (4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dimethylbutan-2-one with a melting point of 135 ° C.

The 1-bromo-1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one used as starting material is obtained from 4-chlorophenol and bromine pinacoline and subsequent bromination with bromine at 140 ^° C. (melting point
80 ^G C).

Claims (1)

26 OO 800 Claim: Method for combating fungi in the household sector, characterized in that one l- (4-chlorophenoxy) -l-imidazolyKl) -3,3-dimethyrdutan-2-one the formula -0 - CH- CO - C (CH * N to act on mushrooms or their habitat.