Note: Descriptions are shown in the official language in which they were submitted.
The invention relates to the use of 1-aryL-3-
hydroxy-3-alkyl-4-(1,2,4-triazol-1-yl)-butane derivatives
as active compounds in microbicidal agents for the pro-
tection of industrial materials.
It is known that triazol and imidazol fungicides
can be used for the protection of plants and seed (cf.
European patent specification 0,040,345~. However, it is
also known that the action of these fungicides has de-
ficiencies (cf. European patent specification 0,180,313).
They are therefore unsuitable for the protection of
industrial materials against fungal infestation, since
industrial materiaLs are always subject to attack by a
large number of different types of fungi, so that reliable
protection can only be achieved using fungicides having a
broad spectrum of action or using fungicide combinations
which are composed in such a manner that a broad spectrum
of action is produced. Triazol fungicides having a de-
ficient spectrum of action are, for example, triadimefon,
triadimenol and dichlobutrazol (in this respect see Table 2
in the experimental part).
It has been found that certain 1-aryl-3-hydroxy-3-
alkyl-4-(1,2,~-triazol-1-yl) butane derivatives of the
formula
0~1
~ H2-CH2-C-Alkyl
CIH2
in which
X represents halogen, alkylthio having 1 to 6
carbon atoms, or halogenoalkoxy having 1 or 2
carbon atoms and 1 to 5 halogen atoms, and
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: `~k
alkyl represents an alky~ group having 1 to 4 car-
bon atoms,
and also the acid addition salts and metal salt
complexes thereof
can be used as active compounds in the microbicidal agents
for the protection of industrial materials against damage
or destruction by microorganisms~
Compounds of the abovementioned general formula
are preferably used in which X represents halogen, such as
fluorine, chLorine and bromine, and alkyl denotes methyl,
ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert.-
butyl, preferably methyl, ethyl and tert.-butyl.
The following 1-aryl-3-hydroxy-3-alkyl-4-t1,2,4-
triazol-1-yl)-butane derivatives are very particularly
preferably used:
1-(4-chloro-)phenyl-3-hydroxy-3-tert.-butyl-4-(1,2,4-
triazol-1-yl)-butane,
1-(4-bromo-)phenyl-3-hydroxy-3-tert.-butyl-4-(1,2,4-
triazol-1-yl)-butane, and
1-(4-fluoro-)phenyl-3-hydroxy-3-tert.-butyl-4-(1,2,4-
triazol-1-yl)-butane.
The compounds according to the invention can form
addition salts with the following acids: hydrohalic acids,
such as hydrochloric acid and hydrobromic acid, furthermore
Z5 phosphoric acid, nitric acid, sulphuric acid, mono- and
bifunctional carboxylic acids, such as acetic acld, maleic
acid, succinic acid, fumaric acid, tartaric acid, citric
acid, salicylic acid, sorbic acid and lactic acid, and also
sulphonic acids, such as p-toluenesulphonic acid and 1,5-
naphthalenedisulphonic acid.
The following metals can form metal salt complexeswith the compounds according to the invention: the metals
of main groups II to IV and of the subgroups I and II, and
also IV to VIII, of the periodic system. Copper, zinc,
manganese, magnesium, tin, iron and nickel are preferred.
Suitable anions of the salts are those which are
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~,8~ '4
preferably derived from the following acids: hydrohalic
acids, such as hydrochloric acid and hydrobromic acid, fur-
thermore phosphoric acid, nitric acid and sulphuric acid.
The aryl-3-hydroxy-3-alkyl-4-(1,2,4-triazol-1-yl)-
butane derivatives according to the invention, and also theacid addition salts and metal salt complexes thereof, may
be prepared by known processes, for example as specified in
European Patent 40,345.
Surprisingly, the compounds, according to the
invention, of the above mentioned general formula have,
compared to the structurally comparable, known triazol
fungicides, such a broad spectrum of action and are so
effective that they can be used with advantage as micro-
bicides for the protection of industrial materials (in this
respect see comparison Table 2). They do not cause stain-
ing and are compatible with all known paint formulations
(cf. Example 3).
Surprisingly, the compounds according to the
invention additionally represent better, antimicrobially
more active materials-protection substances than the
dithiocarbamates, known from the state of the art, which
likewise have a broad spectrum of action and therefore
represent the closest class of compounds with respect to
the action. However, they are not only less effective than
the compounds according to the invention, but are also
inherently less stable than them. However, stability is a
particularly important property for materials-protection
substances (in this respect, see Example 3).
According to the invention, industrial materials
are non-living materials which have been prepared for use
in technology. For example, industrial materials which are
to be protected against microbial modification or destruc-
tion by active compounds according to the invention may
be adhesives, glues, paper and cardboard, textiles,
leather, wood, paints and plastic articles, cooling lubri-
cants and other materials which can be infested or
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,
,
5f~
decomposed by microorganisms. In the context of the ma-
terials to be protected, parts of production plants, for
example cooling water circuits, which can be impaired by
the multiplication of microorganisms, may also be men-
tioned. In the context of the present invention, ad-
hesives, glues, papers and cardboards, Leather, wood,
paints, cooling lubricants and plastic articles may pref-
erably be mentioned as industrial materials.
Bacteria, fungi, yeasts, algae and mucoorganisms
may be mentioned, for example, as microorganisms which
are able to cause degradation or modification of the
industrial materials. The active compounds according to
the invention preferably act against fungi, particularly
mould fungi, fungi which stain wood and fungi which
destroy wood (Basidiomyceta), and also against muco-
organisms and algae.
Microorganisms of the following genera may be
mentioned as examples:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puteanar
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, such as Trichoderma vir;de,
Escherichia, sùch as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.
Depending on the area of application, the active
compounds according to the invention may be converted
into the conventional formulations, such as solutions,
emulsions, suspensions, powders, pastes and granules.
These can be prepared in a known fashion, for
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a~
example by mixing the active compounds with an extender
which comprises liquid solvent and/or solid excipients, if
appropriate using surfare-active agents, such as emulsi-
fiers and/or dispersing agents, it being possible, if
appropriate, to use organic solvents, such as alcohols, as
adjuvants in the case of the use of water as extender.
Liquid solvents for the active compounds may be,
for example, water, alcohols, such as lower aliphatic
alcohols, preferably ethanol or isopropanol, or benzyl
alcohol, ketones, such as acetone or methyl ethyl ketone,
liquid hydrocarbons, such as petroleum fractions, and
halogenated hydrocarbons, such as 1,2-dichloroethane.
The microbicidal agents used for the protection of
industrial materials generally contain the active compounds
in an amount of 1 to 95% by weight, preferably from 10 to
75% by weight.
The applicational concentrations of the active
compounds according to the invention depend on the type and
occurrence of the microorganisms to be combated, and also
on the composition of the material to be protected. The
ideal use amount can be determined by series of tests. In
general, the applicational concentrations are in the range
from 0.001 to 5% by weight, preferably from O.OS to 1.0%
by weight, relative to the material to be protected.
The active compounds according to the invention may
also be present as a mixture with other known active com-
pounds. The following active compounds may be mentioned as
examples: benzyl alcohol mono(poly)hem;formal and other
formaldehyde-releasing compounds, benzimidazolyl methylcar-
bamates, tetramethylthiuram disulphide, zinc salts of
dialkyl dithiocarbamates, 2,4,5,6-tetrachloroisophthalo-
nitrile, thiazolylbenzimidazol, mercaptobenzthiazol, 2-
thiocyanatomethylthiobenzthiazol, methylene bisthiocyanate,
phenol derivatives, such as 2-phenylphenol, (2,2'-dihy-
droxy-5,5'-dichloro)-diphenylmethane and 3-methyl-4-
chloro-phenol, organo tin compounds, N-trihalogeno-
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~848S~
methylthio compounds, such as folpet, fluorfolpet and
dichlofluanid.
Use examples
Example 1
S In order to determine the activity against -fungi,
the minimum inhibition concentrations ~MIC) of active
compounds according to the invention are determined:
An agar which is prepared from wort and peptone is
treated with active compounds according to the invention
in concentrations from 0.1 mg/l to 5000 mg/l. After the
solidification of the agar, contamination using pure cul-
tures of the test organisms listed in the table is effec-
ted. After storing for two weeks at 28C and S0 to 70%
relative air humidity, the MIC is determined. MlC is the
lowest concentration of active compound at which no growth
caused by the type of microbes used occurs, and is stated
in Table 1 below. MIC values of comparison substances are
listed in Table 2.
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Example 2
A mixed culture of green, blue and brown algae and
diatoms (Stichococcus bacillaris Naegeli, Euglena gracilis
Klebs, Chlorella pyrenoidosa chick, Phormidium foveolarum
Gomont, Oscillatoria geminata Meneghini and Phae odactylum
tricornutum Bohlin) is placed, with bubbling through of
air, in Allen's nutrient solution (Arch. Mikrobiol. 17, 34
to 53 (1952)), which contains 0.2 g of ammonium chloride,
4.0 9 of sodium nitrate, 1.0 9 of dipotassium hydrogen
phosphate, 0.2 9 of calcium chloride, 2.05 g of magnesium
sulphate and 0.02 g of iron chloride in 4 litres of sterile
water. After 2 weeks, the nutrient solution is stained
deep green-blue by intensive algal growth. The destruction
of the algae after the addition of active compounds
according to the invention is recognized by the decolori-
zation of the nutrient solution.
Table 3
Algae-destroying concentrations (mg/l) of the
substances specified below
Active compound from Destructive concentration
Table 1 in mg/l
I 75
25 II 75
III 100
l'HCl 100
Example 3
Test of the mould resistance of paints~
The test is carried out as follows in accordance
with Report 219 of the Defense Standards Laboratories
Maribyrnong/Australia:
The paint to be tested is applied to both sides of
a suitable base.
In order to obtain practice-related results, part
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85~
of the test objects are leached out using running water
(24 hours; 20C) before the mould resistance test;
another part is treated with a stream of warm fresh air
(7 days; 40C).
The test objects thus prepared are placed on an
agar nutrient medium. The test object and the nutrient
medium are contaminated with fungal spores. The test
objects are assessed after storing from 1 to 3 weeks at
20 + 1C and 80-90% relative air humidity. The paint is
long-term mould-resistant if the test object remains free
of fungi or at most a slight edge infestation can be
observed.
Fungal spores of the follo~ing nine mould fungi,
which are known as paint destroyers or are frequently
encountered on paints, are used for the contamination:
1. Alternaria tenuis
2. Aspergillus flavus
3. Aspergillus niger
4. Aspergillus ustus
5. Cladosporium herbarum
6. Paecilomyces variotii
7. Penicillium citrinum
8. Aureobasidium pullulans
9. Stachybotrys atra Corda
0 to 1.5%, relative to the total solids content,
of 1-(4-chlorophenyl)-3-hydroxy-3-tert.-butyl-4-t1,2,4-
triazol-1-yl)-butane (I), are ditributed homogeneously in
samples of a commercially available latex paint based on
polyvinyl acetate.
For comparison, samples are prepared which contain
0 to 5% of tetramethylthiuram disulphide (TMTD).
Paint coats are prepared from the paint samples
and tested for mould resistance by the method described
above.
Result:
paints which contain 0.5% of I have excellent mould
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54
resistance, even after the abovementioned tests.
In contrast, TMTD-containing paints are only mould-
resistant if they contain 4% o-f TMTD. However, such paints
are stained yellow after treatment (leaching out) with
iron-containing water.
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