NO821694L - FUNGICID AGENT FOR MATERIAL PROTECTION. - Google Patents

Abstract

1. Use of 1-iodo-1-alkynols of the formula see diagramm : EP0066769,P7,F2 in which X**1 , X**2 and X**3 are identical or different and denote hydrogen, fluorine, chlorine or bromine, n represents the numbers 0 or 1 and R**1 denotes lower alkyl with 1 to about 6 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, halogen-substituted lower alkyl with 1 to about 6 carbon atoms or a hydrocarbon radical which has 1 to about 6 carbon atoms and is substituted by 1 to 3 phenyl radicals or a hydrocarbon radical which has 1 to about 6 carbon atoms and is substituted by 1 to 3 phenoxy radicals, it being possible for the phenyl and phenoxy radicals to be substituted by halogen, lower alkyl, halogenalkyl, halogenalkoxy or phenyl, for protection against fungi which destroy or discolour wood.

Description

The invention relates to the use of 1-iodo-1-alkynols as fungicidal agents for the protection of technical materials.

From EEP 0002.679, l-halogen-l-propen-3-ols and their use for combating Phytophtora infestans as well as venturia types are also known. They can also be used to combat grain diseases such as grain rust and wheat blight. Surprisingly, it has been shown that a number of 1-iodo-1-alkynols are particularly suitable for the protection of technical materials. A microbicidal agent containing 1-iodo-1-alkynols with the formula was therefore found

in which

12 3

X , X and X are the same or different and mean hydrogen,

fluorine, chlorine or bromine

n means the numbers 0 or 1 and

R" means lower alkyl, cycloalkyl, halogen-substituted lower alkyl or optionally substituted aralkyl or aryloxyalkyl.

According to the invention, lower alkyl generally means a straight or branched hydrocarbon residue with 1 to approx. 6, preferably with 1 to 4 carbon atoms. Examples include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.

According to the invention, cycloalkyl generally means a cyclic hydrocarbon residue with 3-7, preferably 5 or 6 carbon atoms. Examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

Halogen-substituted lower alkyl generally means, according to the invention, one with 1 to 5, preferably 1 to 3, fluorine, chlorine, bromine or iodine atoms substituted straight or branched hydrocarbon residue with 1-6, preferably 1-4 carbon atoms. Examples include: trifluoromethyl, trichloromethyl, difluorochloromethyl, fluorodichloromethyl.

According to the invention, aralkyl generally means one with 1-3, preferably an aryl residue, preferably a phenyl residue, substituted hydrocarbon residue with 1 to approx. 6, preferably 1-4 carbon atoms. Examples include: benzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl, 2,6-dichlorobenzyl, 4-fluorobenzyl, 4-methoxybenzyl, 4-methylbenzyl, 2-chloro-4-methylbenzyl .

According to the invention, aryloxyalkyl generally means one with 1-3, preferably one, aryloxy acid residue, preferably phenoxy residue, substituted hydrocarbon residue with 1 to approx. 6, preferably 1-4 carbon atoms. Examples include: phenoxymethyl, 4-chlorophenoxymethyl, 3,4-dichlorophenoxymethyl, 2,4-dichlorophenoxymethyl, 4-fluorophenoxymethyl, 2,6-dichlorophenoxymethyl.

The aryl part of the aralkyl and aryloxyalkyl residues may optionally also be substituted with further common residues. Examples include: Halogen, preferably fluorine, chlorine or bromine, lower alkyl, preferably methyl, ethyl, propyl and isopropyl, haloalkyl, preferably methyl or ethyl, which is substituted with 1-3 halogen atoms, preferably fluorine or chlorine, especially trifluoromethyl, trichloromethyl .

phenyl.

Generally, the aryl moiety may be substituted with 1-3 additional residues.

Preferred microbicidal agents according to the invention for the protection of technical materials contain 1-iodo-1-alkynols of the formula

in which

12 3

X , X and X have the above meaning and

R 2 means an alkyl residue with 1-6 carbon atoms, a cycloalkyl residue with 3-7 carbon atoms, a straight-line or branched hydrocarbon residue with 1 to approx. 6 carbon atoms,

an optionally substituted aralkyl residue in the aryl part with 1 to approx. 6 carbon atoms in the alkyl part or

an optionally substituted aryloxyalkyl residue in the aryl part with 1 to approx. 6 carbon atoms in the alkyl part.

In particular, the microbicidal agents according to the invention are preferred for the protection of technical materials containing 1-iodo-1-alkynols of the formula

in which

X"*" has the above meaning,

X 4 represents hydrogen, fluorine or chlorine,

X^ means hydrogen or chlorine,

R 3 means methyl, ethyl, isopropyl, tert-butyl or cyclo-hexyl.

1-Iodo-1-alkynol according to the invention can be prepared by

mixes corresponding 1-propionols with iodine in the presence of an aqueous alkali hydroxide solution and optionally in the presence of a diluent.

The incorporation of the active substances in materials that are exposed to attack by fungi and bacteria inhibits the growth of fungi and bacteria, thus maintaining the material's original value. The compounds are non-volatile, water-insoluble, light-insensitive and thermostable, so that they are stable in such materials for a long time.

Technical materials within the scope of the present invention are products that do not themselves occur in nature, but are produced from natural or synthetic starting materials. The products to be protected within the scope of the present invention are technical materials that can be decomposed with the help of microorganisms.

Technical materials which are to protect the substances according to the invention from microbial change and destruction are, for example, adhesives, glue, paper and cardboard, textiles, leather, wood, coating agents, plaster, cooling lubricants and plastic articles which can be attacked and decomposed by microorganisms. Within the framework of the materials that can be protected, parts of production facilities such as cooling water and cooling lubricant circuits, whose functionality can be affected by microorganisms, must also be mentioned. Preferably, the active substances according to the invention can be used for the protection of adhesives, paper, cardboard, iron-on films, wood and the like.

Microorganisms that can cause a breakdown or a change in the technical materials are, for example, bacteria, fungi, yeast, algae, mucus and viruses. Preferably, the substances according to the invention act against fungi and bacteria by the fungicidal effect, molds are also included, wood-destroying and wood-discoloring fungi are also included.

For example, micro-organisms of the following should be mentioned

species:

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus,

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Cheatomium, such as Chaetomium globosum,

Coniophora, such as Coniophora cerebella,

Lentinus, as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Pullularia, such as Pullularia pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride.

Depending on their area of application, the substances according to the invention can be transferred in the usual formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These can be produced in a manner known per se, e.g. by mixing the active substances with a thickening agent consisting of liquid solvent and/or solid carriers, optionally using surface-active agents such as emulsifiers and/or dispersing agents, for example in the case of using thickening agents, organic solvents can optionally be used which co-solvents.

Organic solvents for the active substances can for example be alcohols, such as lower alcohols, preferably ethanol or isopropanol or benzyl alcohol, ketones such as acetone or methyl ethyl ketone, liquid hydrocarbons such as petrol fractions, chlorinated hydrocarbons such as 1,2-dichloroethane.

The microbicidal agents according to the invention generally contain 10-100% by weight, preferably 50-80% by weight of 1-iodo-1-alkynols as active substance.

The application concentration of the substances according to the invention depends on the type and occurrence of the micro-organisms to be combated and on the composition of the material to be protected. The optimal amount used can be determined by trial series. Generally, the application concentration is in the range from 0.001 to 5% by weight, preferably from 0.05 to 0.5% by weight, referred to the material to be protected.

The new active substances according to the invention can also be present in a mixture with other known active substances. For example, the following active substances should be mentioned: benzimidazolyl-methylcarbamate, tetramethyl-thiuram disulfide, N-fluorodichloro-methylthio-phthalimide and N,N-dimethyl-N1-phenyl-(N1-fluorodichloro-methylthio)-sulfamide, formaldehyde-releasing compounds such as hemiformals and oxazolidines, hexahydro-s-triazines, N-methylolamides and phenol derivatives, as well as p-chloro-m-cresol, 2-phenyl-phenol, (2,2'-dihydroxy-5,5<1->dichloro)-diphenylmethane.

Manufacturing examples

Example 1

In a solution of 180.6 (1 mol) 3-(4-chlorophenyl)-1-butyn-3-ol in 2000 ml of methanol, 266.5 g (1.05 mol) of iodine are introduced in portions at 10-15°C and thereby adding 400 ml of concentrated caustic soda at the same time. After three hours, the reaction mixture is stirred into 2 liters of water and thereby the separated oil is taken up in 500 ml of vinegar. The acetic ester phase is washed three times with 50 ml of water each time, dried over anhydrous sodium sulphate and then evaporated under reduced pressure. The remaining oil crystallizes by extraction with petroleum ether. 230 g (75% of the theoretical) of 1-iodo-3-(4-chlorophenyl)-1-butyn-3-ol are thus obtained as colorless crystals of melting point 84-85°C.

Example 2

To a solution of 58.4 g (0.3 mol) 4-(4-chlorophenyl)-1-pentin-4-ol in 600 ml of methanol, at 20-25°C under slight external cooling, 144 ml of concentrated caustic soda are added dropwise and thereby simultaneously introduce 91.5 g (0.36 mol) of iodine in portions. After 8 hours, the reaction mixture is stirred into 1.5 liters of water. The mixture is extracted twice with 250 ml of acetic acid each time, the organic phase is washed with water and the solvent is distilled off under reduced pressure. Thus, 85 g (88.4% of the theoretical) of 1-iodo-4-(4-chlorophenyl)-1-pentyn-4-ol are obtained as a slightly yellow colored oil of refractive index nD 20: 1.6078.

In a similar way, the following examples are obtained with the general formula (I):

Apply! six examples

Example 22; Effect against fungi.

In an agar made from beer wort and peptone, the compound according to the invention was incorporated in stepped concentrations between 1 and 5000 mg/l test sample. After solidification of the agar, the contamination of the thus prepared agar samples took place with a pure culture of different test fungi (see the table).

After two weeks of storage at 28°C and 60-70% relative humidity, they were evaluated. In the table, the minimum inhibitory concentration (MIC) is the smallest concentration of the substance contained in an agar sample, where no growth took place in the species used.

In this sample, e.g. the following compounds a very good effect:

Compounds according to production examples 1 and 2.

Example 23

Effect against bacteria

An agar containing broth as nutrient medium is mixed with the active substances according to the invention in concentrations from 1-5000 ppm. The nutrient medium is then infected each time with Escherichia coli or Staphylococcus aureus and the infected medium is kept for two weeks at 28°C and 60-70% relative humidity. MHK is the lowest concentration of active substance, where no growth takes place with the microbe types used.

In this test, compounds according to manufacturing examples 1 and 2 are used.

Claims (5)

1. Microbicidal agent for the protection of technical materials containing 1-iodo-1-alkynols with formula in which 12 3 X , X and X are the same or different and mean hydrogen, fluorine, chlorine or bromine, n means the numbers 0 or 1 and R"*" means lower alkyl, cycloalkyl, halogen-substituted lower alkyl or optionally substituted aralkyl or aryloxyalkyl. 2. Microbicidal agent for the protection of technical materials according to claim 1 containing in which 12 3 X, X and X have the meaning mentioned in claim 1 and R 2 means an alkyl radical with 1 to approx. 6 carbon atoms, a cycloalkyl radical with 3-7 carbon atoms, one with 1-5 halogen atoms substituted straight or branched hydrocarbon residue with 1 to approx. 6 carbon atoms, an optionally substituted aryloxyalkyl residue in the aryl part with 1 to approx. 6 carbon atoms in the alkyl part. 3. Microbicidal agent for the protection of technical materials according to claims 1 and 2 containing 10 to 100% by weight of the active substance. 4. The use of 1-iodo-1-alkynols of formula in which 12 3 X , X and X are the same or different and mean hydrogen, fluorine, chlorine or bromine, n means the numbers 0 or 1 and R means lower alkyl, cycloalkyl, with halogen substituted lower alkyl or optionally substituted aralkyl or alkoxyalkyl for the protection of technical materials. 5. Use of 1-iodo-1-alkynols according to claim 4, in application concentrations in the range from 0.001 to 5% by weight, referred to the material to be protected.