DE2600800A1 - FUNGICIDALS FOR MATERIAL PROTECTION - Google Patents

Description

The present invention relates to the use of the known 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3,3-dimethylbutan-2-one as a fungicidal agent in material protection, especially in the household and commercial sector.

It has already become known that 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3 _/ 3-dimethylbutan-2-one shows a good spectrum of activity against human, animal and phytopathogenic fungi and is microbicidal (see German Offenlegungsschriften 2 105 490 / Le A 13 458 / and 2 325 156 / Le A 14 999_7). In addition, it is already known that 2- / N- (trifluoromethyl) -N- (fluorodichloromethylthio) -aminoZ-benzoic acid salicylester (active ingredient of the commercial product ^ EULAN ASEPT P) is used as a disinfectant in the household sector (cf. German Offenlegungsschrift 1 919 180 / Le A 12 136 /). However, its effect is not always entirely satisfactory, especially against molds and sprouts.

It has been found that 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3,3-dimethylbutan-2-one the formula

Le A. 16 895 709828/0945

with good success as a fungicidal agent in material protection, in particular can be used in the household and commercial sector with a preventive and fungal effect.

Surprisingly, this shows 1- (4-chlorophenoxy) -1-imidazolyl- (1} -3,3-dimethylbutan-2-one especially against the groups of fungi to be combated in the protection of materials a better effect than the 2- / N- (trifluoromethyl) -N- (f luordichloromethylthio) -amino_7-benzoic acid salicyl ester, which has been used for antimicrobial finishing for some time and is an active ingredient with the same active ingredient type. Since the substance that can be used according to the invention has a particularly broad spectrum of activity with a high intensity of action, in particular against mold, while having favorable physical properties at the same time, is a successful one Use in material protection guaranteed. This represents an enrichment of the technology.

The 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3,3-dimethylbutan-2-one to be used according to the invention is known (see above German Offenlegunsschriften).

The incorporation of the active ingredient into materials that are exposed to attack by fungi 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 is stable over long periods of time in such materials. Examples of materials adversely affected by fungal growth are lime paints, emulsion paints, wallpaper, tile wall joints, furniture, leather, artificial leather, bath mats, shower curtains, textiles, carpeting and tent equipment.

Le A 16 895 - 2 -

709828/0945

In particular, the following types and classes of fungi occur in material protection:

1) Wood: Basidiomycetes

Ascomycetes

Fungi imperfecti

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

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

3) Textiles and leather:

Molds (Aspergillus, Penicillium,

Verticillium et al.)

Mold rot fungi

These lead to a decrease in the strength of fibers and leather, as well as discoloration (mold stains on textiles, red discoloration of Chrome leather)

4) Paints, glue, bitumen:

Molds

Blue fungi

which lead to discoloration by degradation of the dyes or by run own dye production.

Le A 16 895 - 3 -

709828/0945

Particularly noteworthy is the high intensity of action compared to the Pityrosporum ovale, which belongs to the sprout fungi Molds like Aspergillus niger, Penicillium commune, Erysiphe graminis and against Fungi imperfect! how Colletotrichum coffeanum, as well as the sporicidal effect at concentrations of 10 mcg / ml against dermatophyte and Aspergillus spores. The compound shows a high intensity of action in vitro with a primarily fungistatic type of action, i.e. it inhibits the growth of fungi; Fungicidal effects (fungal 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 Form or with a carrier, e.g. dispersed on a finely divided solid or 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 working methods, the products can be used as active ingredients in solvent solutions, Oil-in-water or water-in-oil emulsions are used will. The mixtures can be formulated as concentrates and then with other liquid or solid auxiliaries can be diluted to make the finishing mixture. Good results are obtained in particular when using mixtures containing 0.5 to 3% active ingredient.

The many possible uses are based on the following Examples:

Le A 16 895 - 4 -

709828/0945

Example A ; MIC values for pathogenic fungal species and bacteria that are important in material protection.

Pilζ groups Mushroom species

MIC values in mcg / inl

Dermatophytes Trichophyton mentagrophytes
rubrum
verruscosum
Epiderrnophyton floccosum
Microsporon canis
felineum 1
1
1
1
1
1 Sproi mushrooms Candida albicans
tropicalis
pseudotropicalis
krusei
Torulopsis glabrata
Cryptococcus neoformans 1
1
1
1-4
4th
1-4 Pityrosporum ovale 0.25-0.5 Biphasic
mushrooms Histoplasma capsulatum
Coccidiodes immitis
Sporothrix Schenckii 1
1
2 Molds Aspergillus fumigatus
Niger
Penicillium comune
Madurella grisea H H H ivi Fungi imperfect! Cercospora musae
Collectotrichum "eoff. 5
5-10 Basidiomycetes Hypnochus sasakii 10 (MIC 50) bacteria Staphylococcus aureus 50 Le A 16 895 Streptococci
- 5 - 100 709828 / 094B

Example B ; Reciprocal germ inhibition values compared to Eulan Asept P, as a commercial product with the same direction of action

preparation

Bact. Staphylo-Saccha- Candida mesen- coccus romyces albicans tericus aureus spec.

^ VO-CH-CO-C (CH ₃ ) ₃ 14500 18000

80000

80000

Eulan Asept P

3Om commercial product

3000 30000

60000

30000

Asper- Aspergillus gillus terreus niger

Tncho- Paecilo- Penis phyton myces cillium mentagro- varioti cameru- phytes nonsense

18000 42000 80000 80000

80000

<3000

3000 30000 <3000

30000

Le A 16 895

7098 28/0945

Example C: Equipment of shoe midsole material

Experimental set-ups;

Jiontaminati ^ n ^ test

A 3x3 cm piece of the plastic midsole material, which contains 1.5 percent by weight Vifirkstoff in addition to an empty control, was placed in damp chambers, soaked with Nervina malt solution and with about 2-3xlO ³ germinable particles or cells of

Trichophyton mentagrophytes Trichophyton rubrum as prototypes for dermatophytes,

Candida albicans as a key germ for yeast,

Aspergillus fumigatus and Penicillium comune as a representative of the mold group.

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

2) Agar diffusion test

Pieces of the midsole material approximately 1 x 1 cm in size were placed in Petries dishes and covered with Sabouraud agar. After the agar had solidified, IxIO ^{5 became} infectious particles of the fungal species

Trichophyton mentagrophytes Trichophyton rubrum Candida albicans Aspergillus fumigatus and Penicillium comune

Le A 16 895 - 7 -

709828/0945

suspended in 0.5 ml of physiological saline solution, homogeneous spatula on the Petri dishes and incubated the Petri dishes for 4 days at 28 ° C.

Results :

On the unfinished control material showed
all germs normal growth. The material treated with l- (4-chlophenoxy) -l-imidazolyl- (l) -3,3-d the germs, with Candida an approx. 30% inhibition
of vegetation.

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

-Diffusion test

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

Preparation zones of inhibition in mm 0

Cand.alb. Trich.ment. Trich.rubr. Asp.fum.

control 0 0 0 0 1,596 active ingredient 38 38 38 35 2 % active ingredient 38 46 45 38 3 % active ingredient 41 50 50 39

Le A 16 895 - 8 -

709828/0945

Example D ; Finishing of Lefamaterial (leather fiber)

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

Composition of the material:

70 parts leather fiber 30 parts natural rubber

corresponds to 50 parts

Natural latex 6O%

1.5 parts Vulkanox NKF (an adhesive)

a) 2 resp.

b) 3 parts of active ingredient

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

Result:

Both compositions were fully effective in the contamination test and in the agar diffusion test.

Le A 16 895 - 9 -

709828/0945

tr " Example E ; Household spray

jp 1) Agar plates inoculated with germs are treated with spray formulations (according to Example F):

Spray asp. Permanent niger

Asp. Poecilo-Penic. Trich. Candida Staph. Bac.
terrens myces earner. ment. albicans aureus me sent.

Spray formulation I

1 sec. Without without without without without without without without

Fouling fouling fouling fouling fouling fouling fouling

5 see. ''

I f

I t

I t

t t

t t

Sprayi formulation II

1 see.

5 see,

I t I t

I f

1 I.

I I

I t

I t

I I

I I

t I

OO OO O CD-

260080Ö

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

Shoe leather
Textile mixed fabric woodchip wallpaper filter paper

Test germs:

Aspergillus terreus, Trichoderma viride

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

Result ^

With spray times of 1 and 2 seconds. were the above-mentioned germ carriers no vegetation after 14 days.

Le A 16 895 - 11 -

709828/0945

Example F : Aerosol formulations

0.5% 1- (4-chlorophenoxy) -1-imidazolyl- (l) -3.3

dimethylbutan-2-one O ₁ IJi Evergreen 10 745 H + R *> 39.4% isopropanol 60.05-0 Frigen 11/12 (30:70) ** ^J.

Formulation_II

0.5% 1- (4-chlorophenoxy) -1-imidazolyl- (l) -3.3

dimethylbutan-2-one 0.1% evergreen 10 745 H + R * ⁰ 39.4% ethanol
60.0% Friday 11/12 (30:70) **>

0.5% 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3,3-

dimethylbutan-2-one 0.1% Evergreen 10 745 H + R * ^} 59.5% Isopropanol 39.9% Frigen 11/12 (30:70) **)

*> Perfume oil as a fragrance component

*) Frigen 11 = CCl ₃ F; Frigen 12 = CCl ₂ F ₂

Le A 16 895 - 12 -

709828/0945

Manufacturing example ~ AU '2600800

O-CH-CO-C (CH ₃ ) 3

ώ.

12.25 g (0.05 mol) of l-bromo-1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one and 12 g (0.18 mol) of imidazole are refluxed for 18 hours after dissolving in 120 ml of acetonitrile heated to boiling. After the solvent has been distilled off in vacuo, 150 ml of Y / water are added to the residue and the aqueous phase is then treated three times with 30 ml of water each time, dried and the solvent is distilled off in vacuo. After recrystallization of the residue from approximately 400 ml of ligroin, 10.5 g (72 Js of theory) of 1- (4-chlorophenoxy) -l-imidazolyl- (l) -3,3-dimethylbutan-2-one with a melting point of 135 ^{° are obtained} C.

Used as a starting material l-bromo-l- (4-chlorophenoxy) -3,3-dimethyl-butan-2-one from 4-chlorophenol and Brompinakolin and subsequent bromination with bromine at l40 ° C is obtained (melting point 80 ⁰ C).

Le A 16 895

709828/0945

Claims (4)

Patent claims: 1) Fungicidal agent for material protection, characterized by a content of 1- (4-chlorophenoxy) -1-imidazolyl- (1) 3,3-dimethylbutan-2-one of the formula NVo-CH-CO-C (CH ₃ ) ₃ ) ₃ On 2) A method for combating fungi in the protection of materials, characterized in that 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3,3-dimethylbutan-2-one according to claim 1 can act on fungi or their habitat. 3) Use of 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3,3-dimethylbutan-2-one according to claim 1 for combating fungi in material protection. 4) Process for the preparation of fungicidal agents for material protection, characterized in that 1- (4-chlorophenoxy) -1-imidazolyl- (1) -3,3-dimethylbutan-2-one according to Claim 1 with extenders and / or surface-active agents Means mixed up. Le A 16 895 - 14 - 709828/0945 ORIGINAL INSPECTED