Note: Descriptions are shown in the official language in which they were submitted.
Le A 32 273-Foreign countries Lin/Kr/W6/30.09.1997
F I L E, R+Pl-EN T H I S AiN~-~E~--~
T~-T TRANSt,AfIOI~
Fun~icidal benzothiophene-2-carboxamide S,S-dioxides for cutting oils
The application relates to the use of benzothiophene-2-carboxamide S,S-
dioxides,
preferably N-cyclohexylbenzothiopen-2-carboxamide S,S-dioxide, as fungicide in
S cutting oils.
Benzothiophene-2-carboxamide S,S-dioxides (BCDs), a process for their
preparation
and their fungicidal action are known (DE-A-41 15 184). Their activity against
phytotoxic fungi and dermatophytes is described especially. In addition, it is
stated
that BCDs are suitable for the protection of industrial materials against
microbial
change or destruction. Industrial materials mentioned are, inter alia,
coatings. It has
now surprisingly been found that N-alkyl-BCDs are not only active against the
moulds usually growing on coatings, but also have an outstanding action
against the
other types of fungal and yeast populations in cutting oils. Furthermore, BCDs
offer
the advantage over other fungicides employed in this use that, even with
relatively
long service times, no unwanted discoloration phenomena occur. The low
application
rates necessary to control fungal and yeast growth in addition permit an
economic
procedure and thus represent a contribution to increasing environmental safety
and
safety at work.
The application therefore relates to the use of N-alkyl-benzothiophene-2-
carboxamide S,S-dioxides, preferably N-cyclohexyl-benzothiophene-2-carboxamide
S,S-dioxide, for the protection of cutting fluid emulsions against infections
by fungi
and yeasts.
Preference is given to N-alkyl compounds in which alkyl represents methyl,
ethyl,
n- or isopropyl, n-, isobutyl, s- or t-butyl, n- or isopentyl, n- or isohexyl,
n- or
isoheptyl, n- or isooctyl, n- or isononyl, n- or isodecyl, n- or isododecyl, n-
or
isooctadecyl, allyl, n- or isobutenyl, n- or isopentenyl, n- or isohexenyl,
propargyl,
n- or isobutinyl, n- or isopentinyl, n- or isohexinyl, chloromethyl,
bromomethyl,
chloroethyl, bromoethyl, chloropropyl, bromopropyl, cyanomethyl, cyanoethyl,
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-2-
cyanopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl,
methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl,
methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl,
ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl,
propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl; in
addition
cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl,
cyclopentyl,
cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexyl,
cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, each of which is
optionally
monosubstituted to tetrasubstituted in the cycloalkyl moiety, identically or
differently, by fluorine, chlorine, bromine, methyl, ethyl, n- or isopropyl,
chloromethyl, dichloromethyl or trifluoromethyl.
Particular preference is given to N-n-butyl-, N-n-pentyl-, N-n-hexyl-,
N-cyclohexylmethyl-, N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxides.
High particular preference is given to N-cyclohexyl-benzothiophene-2-
carboxamide
S,S-dioxide.
These compounds are distinguished by high activity and low tendency to
discoloration, so that they, in contrast to the other BCDs and other
commercially
conventional fungicides, can also be used in cutting oils over relatively long
periods
of time without losses in action.
Surprisingly, the compounds demonstrate a particularly high microbicidal
activity, in
particular fungicidal action, in conjunction with a broad spectrum of action
against
moulds and yeasts relevant in cutting oils.
Examples, but without being limiting, which may be mentioned are the groups of
fungi and yeasts below:
Aspergillus, such as Aspergillus niger,
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-3-
Candida, such as Candida albicans,
Chaetomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puteana,
Geotrichum, such as Geotrichum candidum,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Acremonium, such as Acremonium strictum,
Aureobasidium, such as Aureobasidium pullulans,
I 0 Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, such as Trichoderma viride,
Fusaria, such as Fusarum solani.
The application likewise relates to mixtures of N-alkyl-BCDs with at least one
further microbicidal or microbiostatic active ingredient.
Owing to this active ingredient combination, the activity spectrum of the
N-alkylbenzothiopen-2-carboxamide S,S-dioxides is further broadened, or
particular
effects are achieved. In many cases this produces synergistic effects. If the
active
ingredient combinations are present in certain weight ratios, the synergistic
effect is
demonstrated particularly markedly. However, the weight ratios of the active
ingredients in the active ingredient combinations can be varied in a
relatively broad
range.
Preferred mixing partners are, for example, the compounds:
N-Methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-
N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylen-
isothiazolinone, 4,5-benzisothiazolinone;
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-4-
formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol
mono(poly)hemiformal, oxazolidines, hexahydro-s-triazines, N-methylolchloro-
acetamide, paraformaldehyde, 1,6-dihydroxy-2,5-dioxohexane, N,N'-dihydroxy-
methyleneurea, N-(2-hydroxypropyl)aminomethanol;
S
thiocyanates such as thiocyanatomethylthiobenzothiazole,
methylenebisthiocyanate;
iodine derivatives such as diiodomethyl-p-tolylsulphone, 3-iodo-2-propinyl
alcohol,
4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethyl
carbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol,
3-iodo-2-propinyl-n-butyl carbamate, 3-iodo-2-propinyl-n-hexyl carbamate, 3-
iodo-
2-propinyl-cyclohexyl carbamate, 3-iodo-2-propinyl-phenyl carbamate;
phenol derivatives such as 3-methyl-4-chlorophenol, 3,5-dimethyl-4-
chlorophenol,
phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol,
2-benzyl-4-chlorophenol;
bromine derivatives such as 3-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-
hydroxy-
acetophenone, 2,2-dibromo-3-nitrilo-propionamide, 1,2-dibromo-2,4-
dicyanobutane,
(3 -bromo-(3-nitrostyrene;
pyridines such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn, Zn salts),
tetra-
chloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;
metal soaps such as tin naphthenate, octoate, 2-ethylhexanoate, oleate,
phosphate,
benzoate; copper naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate,
benzoate; zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate,
benzoate;
dialkyldithiocarbamates such as sodium and zinc salts of
dialkyldithiocarbamates,
tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate;
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-5-
nitrites such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-
dithioimido-
carbamate;
quinolines such as 8-hydroxyquinoline and their copper salts;
benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thio-
phonate methyl, thiabendazoles or their salts;
moropholine derivatives such as tridemorph, fenpropimorph, falimorph,
dimethomorph, dodemorph; aldimorph, fenpropidine and their arylsulphonic salts
such as p-toluenesulphonic acid and p-dodecylphenylsulphonic acid;
dithiocarbamates, cufraneb, ferbam, mancopper, mancozeb, maneb, metam,
metiram,
thiram, zeneb, ziram;
benzothiazoles such as 2-mercaptobenzothiazole;
quinolines such as 8-hydroxyquinoline and their copper salts;
benzamides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamides;
boron compounds such as boric acid, boric ester, borax;
triazoles:
amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole,
fen-
chlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol,
imibenconazole,
isozofos, myclobutanil, Opus, paclobutrazole, penconazole, propioconazole, (~)-
cis-
1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, tebuconazole,
tetracona-
zole, triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole;
imidazoles:
imazalil, pefurazoate, prochloraz, triflumizole.
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-6-
High particular preference is given to mixtures of compounds of the formula
(I) with
N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, n-
octylisothia-
zolin-3-one, benzoisothiazolinone, N-(2-hydroxypropyl)-amino-methanol, benzyl
alcohol(hemi)-formal, glutaraldehyde, Omadine, 1,6-dihydroxy-2,5-dioxohexane,
N,N'-dihydroxymethyleneurea, hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine
and/or 3-iodo-2-propinyl-n-butyl carbamate.
The N-alkyl-BCDs and the active ingredient combinations according to the
invention
have a strong microbicidal action and can be used in practice for controlling
unwanted microorganisms. The N-alkyl-BCDs and the active ingredient
combinations according to the invention are suitable for the protection of
industrial
materials against infestation and destruction by unwanted microorganisms.
Industrial materials are, in the present context, taken to mean non-living
materials
which are prepared for use in industry. For example, industrial materials
which are to
be protected by active ingredients according to the invention against
microbial
change or destruction can be adhesives, sizes, paper and cardboard, textiles,
leather,
wood, coatings and plastics articles, cutting fluids and other materials which
can be
infested or decomposed by microorganisms. In the context of materials to be
protected, parts or production plants, for example cutting fluid circuits,
which can be
impaired by growth of microorganisms, may also be mentioned.
Particular preference is given to industrial materials which comprise water or
are
prepared on a water basis or are processed using water, such as cutting
fluids.
Preferably, the N-alkyl-BCDs are used in cutting fluids, in adhesives, sizes
or in
cutting fluid circuits. In this case, the long-term stability given is of
particularly great
commercial benefit, since in this manner, an adequate protection for many
weeks is
ensured by a single small dosage. Furthermore, the non-occurrence of
discoloration is
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
_7_
advantageous in practice, since as a result the otherwise necessary addition
of
complexing agents can be dispensed with. Finally, there are also ecological
advantages, since compounds from the prior art contain iodine in the molecule,
which iodine accumulates in the material (e.g. cutting oil) due to
decomposition and
then must be disposed of separately.
The N-alkyl-BCDs and the active ingredient combinations according to the
invention
can, depending on their respective physical and/or chemical properties, be
converted
into conventional formulations, such as solutions, emulsions, suspensions,
powders,
foams, pastes, granules, aerosols and very fine encapsulations in polymeric
substances.
These formulations are prepared in a known manner, e.g. by mixing the active
ingredients with extenders, that is liquid solvents, pressurized liquefied
gases and/or
solid carriers, with or without the use of surfactants, that is emulsifiers
and/or
dispersants and/or foam-forming agents. In the case of use of water as an
extender,
for example, organic solvents can also be used as auxiliary solvent. Suitable
liquid
solvents are essentially: aromatics, such as xylene, toluene,
alkylnaphthalenes,
chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as
chlorobenzenes,
chloroethylenes, or methylene chloride, aliphatic hydrocarbons, such as
cyclohexane
or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol or
their
ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl
isobutyl
ketone or cyclohexanone, highly polar solvents, such as dimethylformamide or
dimethyl sulphoxide, as well as water; liquefied gaseous extenders or carriers
is taken
to mean those fluids which are gaseous at standard temperature and at
atmospheric
pressure, e.g. aerosol propellant gases, such as halogenated hydrocarbons as
well as
butane, propane, nitrogen and carbon dioxide; solid carriers which are
suitable are:
e.g. natural rock flours, such as kaolins, aluminas, talcum, chalk, quartz,
attapulgite,
montmorillonite or diatomaceous earths and synthetic rock flours, such as
highly
disperse silicic acid, aluminium oxide and silicates; solid carriers for
granules which
are suitable are: for example crushed and fractionated natural rocks such as
calcite,
CA 02284492 1999-09-08
Le A 32 273-Fore~n countries
_g_
marble, pumice, sepiolite, dolomite as well as synthetic granules from
inorganic and
organic flours and granules from organic materials such as sawdust, coconut
shells,
corn cobs and tobacco stalks; emulsifiers and/or foam-formers which are
suitable are:
for example non-ionogenic and anionic emulsifiers, such as polyoxyethylene
esters
of fatty acids, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl
polyglycol ether,
alkyl sulphonates, alkyl sulphates, aryl sulphonates and protein hydrolysates;
dispersants which are suitable are: for example lignin sulphite liquors and
methylcellulose.
In the formulations, use can be made of adhesion promoters such as
carboxymethylcellulose, natural and synthetic, pulverulent, granular or latex-
form
polymers, such as gum arabic, polyvinyl alcohol), polyvinyl acetate), as well
as
natural phospholipids, such as cephalins and lecithins and synthetic
phospholipids.
Other additives can be mineral oils and vegetable oils.
Use can be made of colours such as inorganic pigments, e.g. iron oxide,
titanium
oxide, ferrocyanide blue and organic colours such as alizarin, azo and
metallophthalocyanine colours and trace nutrients such as salts of iron,
manganese,
boron, copper, cobalt, molybdenum and zinc.
The microbicidal compositions or concentrates used to protect industrial
materials
comprise the active ingredient or the active ingredient combination in a
concentration
of 0.1 and 95% by weight, in particular 1.0 to 60% by weight.
The use level of the active ingredient or active ingredient combinations to be
used
according to the invention depends on the type and occurrence of the
microorganisms
to be controlled and on the composition of the material to be protected. The
optimum
application rate can be determined by test series. Generally, the use levels
are in the
range from 0.001 to S% by weight, preferably from 0.01 to 1.0% by weight,
based on
the material to be protected. When the active ingredients or active ingredient
combinations to be used according to the invention are incorporated into
cutting fluid
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-9-
concentrates, the respective dilution factor with respect to preparation of
the water-
mixed cutting fluid emulsion must be taken into account.
The compositions according to the invention advantageously allow the
previously
available compositions to be replaced by more effective ones. The compositions
according to the invention show a good stability, do not lead to
discolorations and
advantageously have a broad spectrum of activity.
The examples below serve to illustrate the invention. The invention is not
restricted
to the examples.
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-10-
Example 1
Determination of activity in a cutting fluid emulsion
The study is carried out with a mineral-oil-based cutting fluid. The
concentrate is
diluted with water so that a S% strength emulsion results. The active
ingredients to
be tested are incorporated into this formulation in the specified
concentration range.
The resultant samples are then inoculated with bacteria and also a mixture of
moulds
and yeasts (separate solutions). After one week at room temperature, a sample
is
withdrawn to determine the number of surviving microorganisms. Subsequently
thereto, inoculation is repeated, there is a wait of one week and further
processing is
carried out as described. The assay is terminated as soon as the growth of the
microorganisms is no longer controlled by the amount of microbicide added in
the
particular case.
The surviving microorganisms are determined, for bacteria on standard plate
count
agar, for moulds and yeasts on malt extract agar, duplicate determinations
being
carried out in each case.
The microorganisms serving for the inoculation comprise the following
representatives:
Bacteria
Pseudomonas aeruginosa
Pseudomonas fluorescens
Pseudomonas oleovorans
Pseudomonas rubescens
Pseudomonas stutzeri
Alcaligenes faecalis
Citrobacter freundii
Corynebacterium sp.
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
-11-
Moulds
Acremonium strictum
Fusarium solani
Geotrichum
Yeasts
Rhodotorula rubra
The results are shown in the table below:
Table 1
1 2 3 4 5 6 7 8 Weeks
B 10~
~ S02 H~ - _ _ - _ _
according to the invention
M 0 0 0 0 0 0 0 0
Y 0 0 0 0 0 0 0 0
B = Bacteria; M = moulds; Y = yeasts
The table reports the number of colony-forming units per ml (CFU/ml).
Active ingredient concentration: 100 ppm of N-cyclohexylbenzothiophene-2-
carboxamide S,S-dioxide
As Table 1 verifies, addition of the compound according to the invention, even
at low
concentration, leads to the active suppression of the growth of moulds and
yeasts,
this effect remaining over several weeks, after only one addition of active
ingredient
(long-term stability).
CA 02284492 1999-09-08
Le A 32 273-Foreign countries
- 12-
In contrast to the prior art (Na-Pyrion), with the invention according to the
invention
there is no risk of discolorations, even in the case of relatively long use.
CA 02284492 1999-09-08
