DE4032576A1 - New substd. tri:halo:allyl beta-cyanoalkyl ether cpds. - prepn. and use as microbiocide for protection of wood, wood coatings, semi-finished leather goods etc. - Google Patents

Abstract

New substd trihaloallyl beta-cyanoalkyl ethers of formula (I) are claimed. R1, R2 = H or 1-3C alkyl; at least 1 or X, Y and Z= iodine and the other 2 = Br or iodine. USE/ADVANTAGE - Microbiocidal compsns contain (I), opt with other microbiocides, esp 1-98 (10-50) wt% of (I), and are used to protect materials, esp leather, paper, and textile hydrophobising agents, against micro-organisms (claimed). (I) can also be used to protect freshly cut wood, wood coatings, semi-finished leather goods, synthetics, propellants, coolant lubricants, coatings and silicone sealants. (I) have high antimicrobial activity, with a broad spectrum of activity, esp against bacteria (eg Bacillus subtilis), yeasts (eg Torula utilis, Saccharomyces cerevisiae), moulds (eg Ulocladium consortiale, Aspergillus niger, Penicillium funiculosum, Chaetomium glbosum, Trichoderma viride, Sclerophoma pitophila), wood destroying moulds (eg Aureobasidium pullulans, Coniophora puteana, Poria montecola), and algae (eg Chlorella fusca). (I) are hardly water-soluble and nonvolatile, and have low toxicity. More specifically, R1, R2 = H and/or Me. In an example, (A) 23.5 g of 1-iodopropyne-3-yl deta'-cyanoethyl ether, in 100 ml of 1,2-dichloroethane, was reacted in portions with 25.4 g of iodine, followed by stirring at room temp for 16 h. Sepn gave 39.7 g (81%) of 1,1,2-triiodopropen-3-yl beta'-cyanoethyl ether, with mpt 56-58 deg C.

Description

The invention relates to novel substituted trihaloallyl β-cyanoalkyl ethers, their preparation and their Use as microbicides.

Hydrous or weathered technical Materials are derived from microorganisms, such as molds, Yeasts, bacteria or algae colonized and by their metabolic activities damaged.

It is therefore these materials microbiocidal acting Substances too. So far, it was primarily the Effectiveness and less environmental impact or Toxicology of the agents used in the foreground. in the essential therefore chlorinated phenols (pentachlorophenol), Tributyltin esters and formaldehyde-containing preservatives used.

For ecological reasons, the use of these substances be restricted.

There is therefore a great need for sparingly soluble in water, non-volatile, broad against microorganisms acting, low toxicity and little to the environment harmful substances used to protect wood, leather, Textiles, paints, plaster, technical aqueous formulations etc. can be used.

There have already been various iodine-containing trihaloallyl compounds for the protection of technical materials (see Y. Morisawa et al in "Holzforschung", 38, 225 ff. (1984).  

Triiodoallyl alcohol is in the form of a 10% solution the name "DEKABIACE" as a formulation for water treatment in trade (see Japan Chemical Week, October 10, 1985).

Triiodoalkenyl carbamates are called biocides in the European Patent Application 0 015 044 described.

The compounds mentioned have a high antimicrobial Efficacy and low toxicity to warm-blooded animals. But they have the disadvantage that they from the protective materials due to weather conditions their relatively high water solubility and relative washed out high vapor pressure or into the atmosphere be discharged.

The object of the invention was to provide new compounds, which have a high antimicrobial activity and at the same time the above-mentioned disadvantages no longer have.

The problem was solved by new trihaloallyl-β- cyanoalkyl ethers of the general formula I.

wherein R¹ and R² are independently hydrogen or identical or different alkyl having 1 to 3 carbon atoms and at least one of the substituents X, Y or Z stands for iodine, the other two for bromine or iodine. Preferred examples of R¹ and R² are hydrogen and / or Methyl.  

The preparation of the new substituted trihaloallyl β-cyanoalkyl ether of the formula I is carried out by Reaction of the corresponding 1-halopropy-3-yl-β- cyanoalkyl ethers of the formula II with halogens or halogenating Means in the presence of diluents and at temperatures of -20 ° C and + 40 ° C

where X is in particular iodine or bromine.

As the halogen, in particular iodine, bromine, as halogenating Agent, in particular iodobromide or bromine chloride be used.

Diluents are organic solvents, such as Alcohols, e.g. As methanol, ethanol or iso-propanol, halogenated Hydrocarbons such. For example, dichloromethane, trichlorethylene, 1,2-dichloroethane, ethers such as. For example diisopropyl ether, Methyl, t-butyl ether, glycol esters or lower alkyl ethers or others not with the halogens used or halogenating agents reacting solvents.

The solvents can be mixed together in pure form or mixed with water.

The preparation of the necessary as intermediates Halogenpropin- 3-yl-β-cyanoalkyl ether of the formula II with X = I or Br takes place in a manner known per se (for example DE-OS 35 26 789) by reacting the corresponding propyne 3-yl β-cyanoalkyl ethers of the formula II in which X is Hydrogen is alkaline with halogens (iodine or bromine) Conditions in the presence of suitable diluents and at temperatures of -20 ° C and + 40 ° C.

As bases, alkali or alkaline earth hydroxides, such as z. Sodium hydroxide, potassium hydroxide, lithium hydroxide, Calcium hydroxide, or alkali or alkaline earth alcoholates, such as For example, sodium ethylate, sodium propoxide, potassium methylate, Kaliumtertiärbutylat be used; prefers be sodium hydroxide and potassium hydroxide.

Suitable iodinating agents are, besides iodine, alkali iodides in Presence of oxidizing agents, such as. For example, sodium iodide with sodium hypochlorite or calcium hypochlorite. In the preparation of 1-bromopropyne-β-cyanoalkyl ether the starting material is preferably elemental bromine used as brominating agent.

Suitable diluents in the preparation of the starting materials are preferably lower alcohols, such as. B. Methanol, ethanol or iso-propanol used. As well Glycols, their ethers and esters can be used. Examples of glycols are mono- or di- or triethylene glycol, Polyethylene glycol 200-600, mono- or di- or tripropylene glycol, polypropylene glycol 300-600, Mono- or diethylene glycol methyl ether, mono- or diethylene glycol ethyl ether, mono- or diethylene glycol isopropyl ether, Mono- or Dipropylenglykolbutylether, mono- or Dipropylene. The solvents can also mixed or diluted with water used become.

Those needed for the production of the starting materials Propyn-3-yl-β-cyanoalkyl ethers can be prepared according to the known Method of propyn-3-ol and α, β-unsaturated Nitriles are prepared (see Chemical Abstracts, 68, 49 008 (1968)).  

For use as microbicides need the inventive Compounds not to be further purified. If desired, they can with the help of a suitable Solvent with a conventional method such. B. Recrystallization or liquid chromatography isolated become.

The compounds of the invention are in general low melting solids or oils.

The compounds of the invention are characterized by their high efficiency and broad spectrum of activity against microorganisms, especially against bacteria, such as z. B. Bacillus subtilis, yeasts such. Torula utilis, Sacharomyces cerevisae, molds such. B. Ulocladium consortiale, Aspergillus niger, Penicillium funiculosum, Chaetomium globosum, Trichoderma viride, Sclerophoma pityophila, wood-tingling fungi, such. B. Aureobasidium pullulans, wood-destroying fungi, such. B. Coniophora puteana, Poria montecola, algae such. B. Chlorella fusca off.

They are suitable because of their broad spectrum of activity especially for the protection of technical materials, such. B. fresh cut wood, wood coatings, leather, leather semi-finished goods, Plastics, textile hydrophobing, Fuels, coolants, paper, coatings, Silicone sealants.

The microbicides according to the invention can be particularly advantageous incorporated in nonpolar, hydrophobic materials become, from which z. B. from the European Patent Application 15 044 known O-Triiodallyl-N-butylcarbamate separated by crystallization.  

The active compounds are formulated in the usual way as a solution. The formulation contains the active ingredient in one Amount of 1 to 98 weight percent, preferably 10 to 50 weight percent.

Particularly suitable solvents are glycols whose Mono- and diether or their mono- or diesters.

Other suitable solvents especially for nonpolar Systems are: aromatic benzine, xylene, trimethylbenzene; Ketones such as acetone, cyclohexanone, isophorone, methyl isobutyl ketone; Ether, such as. Diisopropyl ether, dimethoxyethane; Esters such. Ethyl acetate, methyl acetate, Acetic acid propyl ester, butyl acetate.

The application concentrations are dependent on the type of protective material and the expected microbial attack between 0.005 and 3%, preferably between 0.05 and 1%, based on the material to be protected.

The active compounds according to the invention can also be used in combination with other known antimicrobial substances be used. For example:

Benzimidazolylmethylcarbamate, quaternary ammonium salts (Quats), such as B. Didecyldimethylammoniumchlorid, Methylenbisthiocyanat, thiocyanatomethylthiobenzothiazole, Iodopropargyl butylcarbamate, tributyltin compounds, 2-Alkylisothiazolinonen such. B. 2-octylisothiazoline 3-one, 2-methylthio-4-tertiarybutylamino-6-cyclopropylamino 1,3,5-triazine.  

example 1

1,1,2-Triiodpropen-3-yl-β'-cyanoethylether

23.5 g (0.10 mol) of 1-iodopropyne-3-yl-β'-cyanoethyl ether (prepared according to DE-OS 35 26 789) are in 100 ml 1,2-dichloroethane in portions with 25.4 g (0.10 mol) of iodine implemented. It is stirred for 16 hours at room temperature, with the iodine is converted. Subsequently, the rotary evaporator distilled off the solvent and the crude product recrystallized from 150 ml of isopropanol. You get colorless crystals.

Yield: 39.7 g (81% of theory)
Melting point: 56-58 ° C
UV (measurement in acetonitrile): 239 nm, ε = 6710
NMR: (measurement at 60 MHz in deuterochloroform)
2.68 ppm - triplet - 2 protons
3.69 ppm - triplet - 2 protons
4.25 ppm - singlet - 2 protons
IR: 2250 cm ^-1 -C≡N
1105 cm ^-1
Content I: found: 78.2% calculated: 77.9%

Example 2

1,1,2-Triiodpropen-3-yl-2'-cyanoprop-1'-yl ether

In an analogous manner, as described in Example 1, receives from 25.0 g (0.10 mol) of 1-iodopropyn-3-yl-2'-cyanopropane 1'-yl ether and 25.5 g of iodine 36.3 g (72% of theory) of 1,1,2-triiodopropene 3-yl-2'-cyanoprop-1'-yl ether as colorless crystals.

Melting point: 50-54 ° C
NMR: (measurement at 60 MHz in deuterochloroform)
1.39 ppm - doublet - 3 protons
2.85 ppm - sextet - 1 proton
3.53 ppm - triplet - 2 protons
4.24 ppm - singlet - 2 protons
IR: 2245 cm ^-1 -C≡N
1105 cm ^-1 COC
Content I: found: 76.0% calculated: 75.7%

Example 3

1-bromo-1,2-diiodpropen-3-yl-2'-cyanoethylether

In an analogous manner as described in Example 1 receives from 11.0 g (58.5 mmol) of 1-bromopropyne-3-yl-2'-cyanoethyl ether and 14.8 g of iodine 20.7 g (80% of theory)  1-bromo-1,2-diiodopropen-3-yl-2'-cyanoethyl ether as colorless crystals.

Melting point: 39-41 ° C
UV (measurement in acetonitrile): 236 nm, ε = 10,770
NMR: (measurement at 60 MHz in deuterochloroform)
2.70 ppm - triplet - 2 protons
3.70 ppm - triplet - 2 protons
4.32 ppm - singlet - 2 protons
IR: 2245 cm ^-1 -C≡N
1105 cm ^-1 COC
Content I: found: 58.1% calculated: 57.4%

Example 4

1-bromo-1,2-diiodpropen-3-yl-2'-cyanoprop-1'-yl ether

In an analogous manner, as described in Example 1, obtained from 15.5 g (76.7 mmol) of 1-bromopropyne-3-yl-2'-cyanoprop-1'-yl ether and 19.5 g of iodine 19.6 g (56% of theory) 1-bromo-1,2-diiodopropen-3-yl-2'-cyanoprop-1'yl ether as a yellow-colored oil.
NMR: (measurement at 60 MHz in deuterochloroform)
1.40 ppm - doublet - 3 protons
2.95 ppm - sextet - 1 proton
3.56 ppm - triplet - 2 protons
4.32 ppm - singlet - 2 protons
IR: 2242 cm ^-1 -C≡N
1117 cm ^-1 COC
Content I: found: 56.0% calculated: 55.7%
Salary Br: found: 17.1% calculated: 17.5%

Example 5

2-bromo-1,1-diiodpropen-3-yl-2'-cyanoethylether

In an analogous manner, as described in Example 1, obtained from 9.8 g (52.1 mmol) of 1-Iodpropin-3-yl-2'cyanoethylether and 10.8 g of iodobromide after recrystallization from gasoline 6.2 g (27 % of theory) 2-bromo-1,1-diiodo-propen-3-yl-2'-cyanoethyl ether as colorless crystals.
Melting point: 52-53 ° C
NMR: (measurement at 60 MHz in deuterochloroform)
2.64 ppm - triplet - 2 protons
3.70 ppm - triplet - 2 protons
4.43 ppm - singlet - 2 protons
IR: 2250 cm ^-1 -C≡N
1105 cm ^-1 COC
Content I: found: 58.6% calculated: 57.4%
Salary Br: found: 17.3% calculated: 18.1%

Example 6

1,2-dibromo-1-iodpropen-3-yl-2'-cyanooethylether

In an analogous manner, as described in Example 1, obtained from 19.6 g (83.4 mmol) of 1-Iodpropin-3-yl-2'-cyanoethyl ether and 13.3 g (83.4 mmol) of bromine 22.7 g (69% of theory) of 1,2-dibromo-1-iodopropen-3-yl-2'-cyanoethyl ether as colorless crystals.
Melting point: 56-58 ° C
UV (measurement in acetonitrile): 224 nm, ε = 10560
NMR: (measurement at 60 MHz in deuterochloroform)
2.65 ppm - triplet - 2 protons
3.67 ppm - triplet - 2 protons
4.47 ppm - singlet - 2 protons
IR: 2252 cm ^-1 -C≡N
1110 cm ^-1 COC
Content I: found: 31.3% calculated: 32.1%
Salary Br: found: 41.0% calculated: 40.5%

Example 7

1,2-dibromo-1-iodpropen-3-yl-2'-cyanoprop-1'-yl ether  

Analogously to Example 1, 7.9 g (31.7 mmol) of 1-iodopropyn-3-yl-2'-cyanoprop-1'-yl ether and 5.1 g of bromine give 7.1 g (57% of theory) of thiol. ) 1,2-bromo-1-iodopropen-3-yl-2'-canoethyl ether as a yellow-colored oil.
NMR: (measurement at 60 MHz in deuterochloroform)
1.37 ppm - doublet - 3 protons
2.87 ppm - sextet - 1 proton
3.56 ppm - triplet - 2 protons
4.44 ppm - singlet - 2 protons
IR: 2242 cm ^-1 -C≡N
1110 cm ^-1 COC
Content I: found: 30.5% calculated: 31.0%
Salary Br: found: 40.0% calculated: 39.1%

Example 8 The effectiveness against fungi Minimal inhibitory concentrations (MIC values)

The microbiocidal effectiveness is determined by determining the minimal inhibitory concentration (MIC values). The MIC value gives the lowest concentration of an active ingredient at which the growth of the test germ is still is completely inhibited. These are graded amounts of active ingredient in dissolved form in liquid nutrient media at 5 ° C incorporated, the nutrient media are then through Cooling solidifies, infects and incubates. It will thus a modified method of determination of bacteriostatic Effect using the dilution test (see Guidelines for Testing of Chemical Disinfectants, Gustav Fischer Verlag, Stuttgart, 2. Edition, 1969, pages 5-6).  

As a breeding ground for mushrooms served Malzagar-N-Nährbodenplatten. The inoculation was carried out with 1 ml of a fungal spore suspension with 10³ germs per ml. After a 14 days long incubation at 29 ° C was the reading of the MIC values in percent by weight, based on the nutrient medium.

table

MIC values against yeast and fungi

Example 9 Efficacy against bacteria Minimal inhibitory concentrations (MIC values)

As a breeding ground for bacteria served standard I nutrient agar plates. The inoculation was carried out with 1 ml of a bacterial suspension, which was mixed with 10³ bacteria per ml. After incubation for 4 days at 37 ° C, the Reading the MIC values in percent by weight, based on the nutrient amount.

table

MIC values against bacteria substance test germ according to Bacillus substilis % example 1 0.0005 Comparative substance: 3-iodopropyn-1-yl-butylcarbamate 0,002

Example 10 Rotting protection equipment of textiles

To the rot proofing equipment of textiles become water-insoluble fungicides in the water repellents incorporated. Prerequisite for the usability of a Fungicides for this application is its miscibility with paraffin. There must be no crystallization occur.

To test the usability as an anti-rotting agent 1.00 g of 1-bromo-1,2-diiodopropen-3-yl-1'-cyanopropane 1'-yl ether (Example 4) with 49 g of paraffin oil at 50 ° C. intensively mixed.  

This gives a clear solution that makes up the active ingredient even when stored at 0 ° C does not further separates. comparatively likewise incorporated 3-iodopropyne-1-yl-1'- cyanoethyl ether (known from DE-OS 35 26 789) is set fast coarsely crystalline.

Example 11 Preservation of coolant emulsions

An emulsion of 5% of a commercial cooling lubricant (pH 8) in water was treated with 1-bromo-1,2-diiodopropene 3-yl-2'-cyanoethyl ether (Example 3) equipped. 200 ml of this emulsion were mixed with 2 g of iron filings. The emulsion was 8 hours daily for 3 weeks shaken.

After 7 days, the emulsion was collected by sampling checked their initial germ content. The emulsion was subsequently a fungal spore suspension of Aspergillus niger, Aureobasidium pullulans and Penicillium funiculosum added, with 10³ germs per ml were entered.

After another 7 days, the germ content of a taken sample and the emulsion second time inoculated. After another 7 days was last the germ count checked.

The determination of the germ count of the samples taken was by evaluating a nutrient plate according to a scale detected with the values 0-4. Where:

0 = no germs
1 = 1 to 10 germs per ml
2 = 11 to 100 germs per ml
3 = 101 to 1000 germs per ml
4 = <1000 germs per ml

As a comparison, a correspondingly conducted investigation, the emulsion being 0.2% 1,3,5-trishydroxy Ethylhexahydrotriazin, as currently standard standard preservation, was added.

The investigations yielded the following result:

Example 12 Conservation of wet blues

Freshly tanned leather (wet blue) is used in aqueous baths each dipped 0.01% of the fungicides to be tested contain.

To test the fungicidal action, the pieces of leather (Wetblue) of about 3.5 × 4 cm size with the grain side placed upside down on a glass bench in a 250 ml jar, its bottom with a moistened paper felt disc is covered. The leather is mixed with 0.5 ml of a mixed spore suspension out

Aspergillus niger
Trichoderma lignorum
Penicillium funiculosum
Chaetomium globosum
Paecilomyces variotii

Mushrooms, isolated from cuddly leather, inoculated, sealed the vessel and stored at 29 ° C.

After seven days of incubation was under the microscope Checked if fungus growth occurs on the leather was.

Inoculation with an identical mixed spore suspension was repeated after 7 days (inoculation # 2).

There were the following criteria for the evaluation of the Growth on the leather used:

0: leather not overgrown
1: Leather slightly overgrown, below 10%
2: leather overgrown, under 30%
3: leather clearly overgrown, below 60%
4: heavily overgrown leather, over 60%

Claims (7)

1. Novel substituted Trihalogenallyl-β-cyanoalkyl ethers of the formula I. in which R¹ and R² independently of one another denote hydrogen or identical or different alkyl having 1 to 3 C atoms and at least one of the substituents X, Y or Z stands for iodine, the other two stand for bromine or iodine. 2. Trihalogenallyl-β-cyanoalkyl ethers according to claim 1, characterized in that R¹ and R² is hydrogen and / or methyl. 3. A process for the preparation of 1-Trihalogenallyl-β-cyanoalkyl ethers of the general formula I given in claim 1, characterized in that a propyn-3-yl-β-cyanoalkyl ether of the formula II wherein X, R¹ and R² have the meanings indicated, is reacted with halogen or halogen-providing agents under alkaline conditions in the presence of a diluent at -20 ° C and + 40 ° C. 4. Microbicidal agents containing one or more Trihalogenallyl-β-cyanoalkyl ethers of claim 1 given formula I, optionally in conjunction with other microbicidal agents.   5. microbicidal agent according to claim 4, characterized in that they contain 1 to 98% by weight, preferably 10 to 50% by weight Trihalogenallyl-β-cyanoalkyl ether of im Claim 1 given formula I included. 6. Use of the microbicidal agents according to claims 4 and 5 for the protection of technical materials. 7. microbicidal agent according to claim 6 for the protection of Leather, textiles, textile hydrophobing against microorganisms.