Note: Descriptions are shown in the official language in which they were submitted.
2~ n~9
The present invention relates to the use of furancar-
boxamides, some of which are known, as microbicides for
the protection of industrial materials.
A large number of furancarboxamides and their use for
combating phytopathogenic fungi have already been dis-
closed (cf. DE-OS (German Published Specification)
2,006,471 and DE-OS (German Published Specification)
2,006,472).
Furthermore, it has already been disclosed that
2,4-dimethyl-5-carboxanilido-thiazole can be used for the
protection of wood against degradation by harmful organ-
isms (cf. DE-OS (German Published Specification)
4,000,349). However, the activity of this substance
leaves something to be desired in some cases, in par-
ticular when low application rates are used.
It has now been found that furancarboxamides of theformula
o
¦¦ ,R4
R2 ~ C N~R5 ( I )
in which
Rl R2 and R3 independently of one another represent
Le A 29 437 - 1 -
~., ~. i:
"r,.^ ~
'.. ,:, :
.', ~
!.~' .
'~ . -
~ 21~2~9
hydrogen or methyl and
R4 and Rs independently of one another represent
hydrogen, alkyl, optionally substituted
phenyl or optionally substituted cyclo-
alkyl,
can be used as microbicides for the protection of indus-
trial materials. ~.
Surpxisingly, the furancarboxamides which can be used
according to the invention are more suitable for combat- :~
ing undesired microorganisms in the protection of
materials than 2,4-dimethyl-5-carboxanilido-thiazole,
which is a previously known active substance of similar
constitution and the same direction of action. ::
Formula (I) provides a general definition of the furan-
carboxamides which can be used according to the inven-
tion.
Rl preferably represents hydrogen or methyl.
R2 preferably represents hydrogen or methyl. ~ :
R3 preferably represents hydrogen or methyl. :~
R4 preferably represents hydrogen, straight-chain or
branched alkyl having 1 to 12 carbon atoms, phenyl
which is optionally monosubstituted to penta-
~7
~, , .
~,
. ~ ,
... .
,: ~
~0?,~9
substituted by identical or different substituents
from the series consisting of halogen, alkyl having
1 to 3 carbon atoms, alkoxy having 1 to 2 carbon
atoms, halogenoalkyl having 1 to 2 carbon atoms and
1 to 5 halogen atoms and/or phenyl, or cycloalkyl
having 3 to 8 carbon atoms, it being possible for
each of these cycloalkyl radicals to be mono-
substituted to trisubstituted by identical or dif-
ferent substituents from the series consisting of
alkyl having 1 to 4 carbon atoms and/or halogen.
Rs preferably represents hydrogen, straight-chain or
branched alkyl having 1 to 12 carbon atoms, phenyl
which is optionally monosubstituted to penta-
substituted by identical or different substituents
from the series consisting of halogen, alkyl having
1 to 3 carbon atoms, alkoxy having 1 to 2 carbon
atoms, halogenoalkyl having 1 to 4 carbon atoms and
1 to 5 halogen atoms and/or phenyl, or represents
cycloalkyl having 3 to 8 carbon atoms, it being
possible for each of these cycloalkyl radicals to be
monosubstituted to trisubstituted by identical or
different substituent~ from the series consisting of
alkyl having 1 to 4 carbon atoms and/or halogen.
Rl particularly preferably also represents hydrogen or
methyl.
R2 particularly preferably also represents hydrogen or
methyl.
~ Le A 2g 437 - 3 -
.~
., ~
~".. .
J.'',
~'` ' '
21~S69
R3 particularly preferably also represents hydrogen or
methyl.
R4 particularly preferably represents hydrogen,
straight-chain or branched alkyl having l to 6
carbon atoms, phenyl which is optionally mono-
substituted to trisubstituted by identical or dif-
ferent substituents from the series consisting of
fluorine, chlorine, bromine, methyl, ethyl, methoxy,
ethoxy, trifluoromethyl and/or phenyl, or represents
cycloalkyl having 3 to 7 carbon atoms, it being
possible for each of these cycloalkyl radicals to be
monosubstituted to trisubstituted by identical or
different substituents from the series consisting of
methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-
butyl, fluorine, chlorine and/or bromine.
Rs particularly preferably represents hydrogen,
straight-chain or branched alkyl having 1 to 6
carbon atoms, phenyl which is optionally mono-
substituted to trisubstituted by identical or dif-
ferent substituents from the series consisting of
fluorine, chlorine, bromine, methyl, ethyl, methoxy,
ethoxy, trifluoromethyl and/or phenyl, or represents
cycloalkyl having 3 to 7 carbon atoms, it being
possible for each of these cycloalkyl radicals to be
monosubstituted to trisubstituted by identical or
different substituents from the series consisting of
methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-
butyl, fluorine, chlorine and/or bromine.
~,
Le A 29 437 - 4 -
... .
'~
-. ~ . . - .
. . .
-~ . . ':
! '
"'''' ~ . ' ' : '
~."'': ' , ~
',,: . : : ~ ' '
' : '
.'.. ,' . ' ,, ''
. ~,;' ' ' .
~1,0~fi~
Examples of the substances which can be used according to
the invention are the furancarboxamides listed in Table
1 below.
Table 1
ll R4
R2 ~ R3N~R5 (I)
Rl R2 R3 R4 R5
_
H CH3 CH3 H -CH3
CH3 CH~ CH3 CH3 -C2H5
CH3 H CH3 H C3H7 n
CH3 H CH3 H -C4H9-t
CH3 CH3 H H ~ 1
CH3 H CH3 H ~ F
. ~
Le A 29 437 - 5 -
~.'
, , . . . , ~ . . . . ...
,.. ::. .
-
21 n2663
Table 1 - continuation ::
R1 R2 R3 R4 R5
' ' '
' ~
CH3 H CH3 H ~ H3
CH3 H CH3 H ~
CH3 H CH3 H ~ F3
CH3 H CH3 H ~ ; ~ :
CH3 H CH3 H Cl
~ -Cl
CH3 H CH
Le A 29 437 - 6 -
,5
.~,'~. :
,~,;l,,
?J~L~2~9
Table 1 - continuation
Rl R2 R3 R4 R5 ~:
CH3 H CH3 H ~
CH3 ~ CH3 H p
The furancarboxamides which can be used according to the
invention are known in some cases (cf. DE-OS (German
Published Specification) 2,006,471 and DE-OS (German
Published Specification) 2,006,472). They can be prepared
by reacting hydroxyketones of the formula
R2~
C~O
¦ (II)
~CH~
~1 OH
in which
and R2 have the abovementioned meanings,
with acetamides of the formula
:1 :
~ Le A 29 437 - 7 -
~ ' , .
;~
:
2~02~9
o
ll R4
CH2-C-N~ 5 (III)
co-R3
in which
R3, R4 and Rs have the abovementioned meanings,
in the presence of a Friedel-Crafts catalyst, such as,
for example, aluminium chloride or aluminium bromide, and
in the presence of an inert organic diluent, such as, for
example, benzene, toluene or xylene, at temperatures
between 20C and 80C. Working-up is carried out by
customary methods. In general, a procedure is followed in
which the reaction mixture is treated with water and
hydrochloric acid, and the organic phase is separated
off, washed and dried and then concentrated. The product
obtained in this process can be freed from any impurities
which may be present, for example by recrystallisation.
The hydroxyketones of the formula (II) or the acetamides
of the formula (III), all of which are required as
starting substances for the preparation, by the above
process, of the furancarboxamides which can be used
according to the invention, or they can be prepared by
~ methods known in principle.
i 20 The active compounds which can be used according to the
invention have a powerful microblcidal activity and can
;
's Le A 29 437 - 8 -
,
,
. :
, ~
2 ~ 3
be employed for protecting industrial materials against
infestation with, and destruction by, undesired micro-
organisms.
Industrial materials in the present context are to be
S understood as meaning non-live materials which have been
prepared for use in industry. For example, industrial
materials which are intended to be protected by active
compounds according to the invention from microbial
change or destruction can be glues, sizes, paper and
board, textiles, leather, wood, paints and plastic
articles, cooling lubricants and other materials which
can be infested with, or destroyed by, microorganisms.
Parts of production plants, for example cooling-water
circuits, which may be impaired by the multiplication of
microorganisms may also be mentioned within the scope of
the materials to be protected. Industrial materials which
may preferably be mentioned within the scope of the
present invention are glues, sizes, papers and boards,
leather, wood, paints, cooling lubricants and heat-
transfer liquids, particularly preferably wood.
The substances which can be used according to the inven-
tion are very particularly preferably suitable for the
protection of wood.
Microorganisms, capable of bringing about degradation of,
or change in, the industrial materials, which may be
mentioned are, for example, bacteria, fungi, yeasts,
algae and slime organisms. The active compounds according
Le A 29 437 - 9 -
. ~
i ,"..
. ;,;-
, .: ~ :
~ .~
- 2 1~ 9
-o ~e l..vention p-e e~ab~ly act agair.st fungi, in pa--
.icular moulds, wood-ciscolouring and wood-destroyins
fungi (Basidiomycetes) and agains~ slime organisms and
algae.
Microorganisms of the following genera may be mentioned
by way of example:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puteana,
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 viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus,
Coriolus, such as Coriolus versicolor,
Stereum, such as Stereum sanguinoleum,
Poria, such as Poria placenta,
Gloeophyllum, such as Gloephyllum trabeum.
Depending on the field of application, the active com-
pounds to be used according to the invention can be
converted into the customary formulations, such as
solutions, emulsions, suspensions, powders, pastes and
Le A 29 437 - 10 -
~ .
, . .
i.,~ . ~
,,; , .
. .
2:~2~
granules.
These can be prepared in a manner known per se, for
example by mixing the active compounds with an extender
composed of a liquid solvent and/or solid carriers,
optionally with the use of surface-active agents, such as
emulsifiers and/or dispersants, where, if water is used
as an extender, organic solvents, such as alcohols, can
optionally be used as auxiliary solvents.
Examples of liquid solvents for the active compounds are
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 benzine fractions, or halogenated
hydrocarbons, such as 1,2-dichloroethane.
The activity and the spectrum of action of the active
compounds which can be used according to the invention,
or of the compositions, concentrates or, quite generally,
formulations prepared herewith, can be increased by
adding, if appropriate, other antimicrobially active
compounds, fungicides, bactericides, herbicides, insec-
ticides or other active compounds for enlarging the
spectrum of action or for achieving specific effects,
such as, for example, additional protection against
insects. These mixtures can have a broader spectrum of
action than the compounds according to the invention.
In many cases, this results in synergistic effects, i.e.
Le A 29 437 - 11 -
:,~........................ .
~:.
~ ~ ,
210~9
the activity of the mixture is greater than the activity
of the individual components. Particularly favourable
components for mixtures are, for example, the following
compounds:
sulphenamides, such as dichlorfluanid (Euparen), tolyl-
fluanid (Methyleuparen), folpet, fluorfolpet;
benzimidazoles, such as carbendazim (MBC), benomyl,
fuberidazole, thiabendazole or salts of these;
thiocyanates, such as thiocyanatomethylthiobenzothiazole
(TCMTB), methylene bisthiocyanate (MBT);
quaternary ammonium compounds, such as benzyldimethyl-
tetradecylammonium chloride, benzyl-dimethyl-dodecyl-
ammonium chloride, didecyl-dimethyl-ammonium chloride;
morpholine derivatives such as Cll-Cl4-4-alkyl-2,6-
dimethyl-morpholine homologues (tridemorph), (~)-cis-
4-[3-tert.-butylphenyl]-2,6-dimethylmorpholine (fenpropi-
morph), falimorph;
phenols, such as o-phenylphenol, tribromophenol, tetra-
chlorophenol,pentachlorophenol,3-methyl-4-chlorophenol,
dichlorophene, chlorophene or their salts;
azoles, such as triadimefon, triadimenol, bitertanol,
tebuconazole, propiconazole, azaconazole, hexaconazole,
prochloraz; l-(2-chlorophenyl)-2-((1-chlorocyclopropyl)-
Le A 29 437 - 12 -
~:,
- 21~5~
3-(1,2,4-triazol-1-yl)-propan-2-ol, 1-(2-chlorophenyl)-
2-(1,2,4-triazol-1-yl-methyl)-3,3-dimethyl-butan-2-ol and
1-(4-chlorophenyl)-1-(1-cyclopropyl-ethyl)-2-(1,2,4-
triazol-l-yl)-ethan-l-ol.
Isopropargyl derivatives such as iodopropargyl butyl-
carbamate (IPBC), iodopropargyl chlorophenylformal,
iodopropargyl phenylcarbamate, iodopropargyl hexyl-
carbamate, iodopropargyl cyclohexylcarbamate, iodopropar-
gyl oxyethylphenylcarbamate;
iodine derivatives, such as diiodomethyl-p-aryl sul-
phones, for example diiodomethyl-p-tolyl sulfone;
bromine derivatives, such as bromopol;
isothiazolinones, such as N-methylisothiazolin-3-one,
5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-oct-
ylisothiazolin-3-one, N-octylisothiazolin-3-one (octili-
none);
benzisothiazolinones, cyclopenteneisothiazolines;
, .~
pyridines, such as 1-hydroxy-2-pyridinethione (and their ~:
sodium, iron, manganese and zinc salts), tetrachloro- :~
4-methylsulphonylpyridine;
metal salts, such as tin naphthenate, copper naphthenate,
zinc naphthenate, tin octoate, copper octoate, zinc
octoate, tin 2-ethylhexanoate, copper 2-ethylhexanoate,
Le A 29 437 - 13 -
, ............ .
~'~
,. . ...
-
'''~,' '' ' ' ~:
;.
h ~ ~
zinc 2-ethylhexanoate, tln oleate, copper oleate, zlnc
oleate, tin phosphate, copper phosphate, zinc phosphate,
tin benzoate, copper benzoate or zinc benzoate, oxides
such as TBTO, CU2O, CuO, ZnO;
organic compounds, such as tributyltin naphthenate and
tributyltin oxide;
nitriles, such as 2,4,5,6-tetrachloroisophthalonitrile
(chlorothalonil) and other microbicides having activated
halogen groups, such as Cl-Ac, MCA, tectamer, bronopol,
bromidox;
benzothiazoles, such as 2-mercaptobenzothiazole; s.o.
dazomet;
quinolines, such as 8-hydroxyquinoline;
formaldehyde-releasing compounds, such as benzyl alcohol
mono(poly)hemiformal, oxazolidines, hexahydro-s-tri-
azines, N-methylolchloroacetamide;
tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(cyclo-
hexyldiazeniumdioxy)-tributyltin or their K. salts, bis- :~
(N-cyclohexyl)diazinium -dioxy- (copper or aluminium);
insecticides which are preferably added are: :
phosphoric esters, such as azinphos-ethyl, azinphos-
methyl, l-(4-chlorophenyl)-4-(O-ethyl, S-propyl)phos-
Le ~ 29 437 - 14 -
rs;~ ' ` ' ~
~f- ~
_,
2 ~ fi ~
phoryloxypyrazole (TiA-230), chlorpyrifos, coumaphos,
demeton, demeton-S-methyl, diazinone, dichlorvos, dimet-
hoate, ethoprophos, etrimfos, fenitrothion, fention,
heptenophos, parathion, parathion-methyl, phosalone,
phoxion, pirimiphos-ethyl, pirimiphos-methyl, profenofos,
prothiofos, sulprofos, triazophos and trichlorfon.
Carbamates, such as aldicarb, bendiocarb, BPMC
(2-(1-methylpropyl)phenylmethylcarbamate),butocarboxim,
butoxycarboxim, carbaryl, carbofuran, carbosulfan,
cloethocarb, isoprocarb, methomyl, oxamyl, pirLmicarb,
promecarb, propoxur and thiodicarb.
Pyrethroids, such as allethrin, bioresmetrin, byfenthrin
(FMC 54 800), cycloprothrin, cyfluthrin, decamethrion,
cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-
3-phenyl-2-methylbenzyl 2,2-dimethyl-3-(2-chloro-2--tri-
fluoromethyl-vinyl)cyclopropanecarbo~ylate, fenpropath-
rin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, ~:
fluvalinate, permethrin and resme~hrin, nitroirnino and nitromethylenes, such as 1-
[6-chloro-3-pyridinyl) methyl] 4,5 dihydro-N-lH-imidazol-2-amine (imidacloprid). I
Organosilicon compounds, preferably dimethyl(phenyl)-
silylmethyl 3-phenoxy-benzyl ethers, such as, for
example, dimethyl(4-ethoxyphenyl)-silylmethyl 3-phenoxy-
benzyl ether or dimethyl(phenyl)-silylmethyl 2-phenoxy-
6-pyridylmethyl ethers, such as, for example,
dimethyl(9-ethoxyphenyl)-silylmethyl 2-phenoxy-6-pyridyl-
methyl ether, or (phenyl)[3-(3-phenoxyphenyl)-propyl]-
Le A 29 437 - 15 -
:~,. . ..
, . ..
.,,~
....
,~;
~-` 21 ~?,669
(dimethyl)-silanes, such as, for example, (4-ethoxy-
phenyl)-[3-(4-fluoro-3-phenoxyphenyl)-propyl]dimethyl)-
silane.
Mixtures of furancarboxamides of the formula (I), an
azole and a quaternary ammonium salt are particularly
preferred.
Other active compounds which are suitable are algicides,
molluscicides, or active compounds against sea animals
which populate, for example, ships' bottom paints.
The microbicidal compositions or concentrates used for
the protection of industrial materials comprise the
active compounds which can be used according to the
invention in a concentration from 0.001 to 95 ~ by
weight, in particular 0.01 to 60 ~ by weight, besides, if
appropriate, 0.001 to 10 ~ by weight of a suitable other
fungicide, insecticide or a further active compound as
mentioned above.
The active compounds, or compositions, which can be used
according to the invention allow the microbicidal com-
positions which had been available to date to be replacedin an advantageous manner by more effective ones. They
exhibit good stability and have, in an advantageous
manner, a broad spectrum of action.
The preparation of active compounds and their use accord-
ing to the invention are illustrated by the examples
Le A 29 437 - 16 -
.. j; ., ,
.,~.
-,
,~ ,s.~, .
:- ., .:
2 ~
which follow.
Preparation Exam le
Example 1
H3C~-NH--O ( I-1 )
H3C H3
133 g (1 mol) of aluminium chloride are added with
stirring at room temperature to a mixture of 354 g
(2 mol) of acetoacetanilide, 176 g (2 mol) of dry acetoin
and 1500 ml of dry toluene. The reaction mixture is
heated slowly to 50C while stirring is continued. Due to
the exothermic reaction, the temperature of the reaction
mixture subsequently rises to boiling point. After the
reaction has subsided, stirring i9 continued for 30
minutes under reflux, the mixture is then allowed to cool
to 80C, and 300 ml of water and 200 ml of 6N hydro-
chloric acid are added. The precipitate obtained is
filtered off, washed in succession with dilute hydro-
chloric acid, water and toluene and subsequently dried.
Upon concentration of the toluene mother liquor, more
product is obtained, which is also filtered off, washed
and dried. In this 2,4,5-trimethyl-3-carboxanilido-furan
is obtained in the form of a colourless solid substance
of melting point 142C.
The furancarboxamides of the formula (I) listed in Table
Le A 29 437 - 17 -
.
, ' ' ,
.'1 ' ' '
' ' ' . ' ~ .
--`` 2~2~S~
2 below are also prepared analogously.
Table 2
~ 4
R2~ 'C-N~
Rl~ ~o ~ R3 ~I)
N~ ~ R ~2 R3 R4 R
2 CH3 H CH3 H ~ ~ 90-9~ C
3 H CH3- CH3 H ~ ~ ~;
4 H H CH3 H ~ ~ 109C
5 CH3 H C~3 H ~ ~ 141-1~3C
¦ Le A 29 437 - 18 -
. .
~, ;,.
~2~
~mp. R 1 R2 R3 R4 R5 P'c~
No. Co~
6 H CH3 CH3 H {~> :
7 H H CH3 ~ --O mp 90-920 C
8 CH3 CH3 C~3 H --O
¦ Use Examples
In the use examples which follow, the compound given
below was employed as comparison substance;
H3 ~ ~ -NH ~
o
(di~closed in DE-OS (German Published specification)
4,000,349)-
Exam~le A
Giant colony te~t
'1
~ Le A 2~ 437 - 19 -
' .
!
, .. ~ . .
,.~, . ~ . . ~
.... ..
210?,669
To demonstrate the activity against wood-destroying
Basidiomycetes, the percentage inhibitory action achieved
in giant colonies of certain species which are treated
with the particular active compounds is determined. To
S this end, an agar is prepared using malt extract and
treated with active compound formulations at certain
concentrations. After the agar has solidified, it is
inoculated with cylindrical agar pieces of diameter 5 mm
which show good growth. The treated agar preparations are
left for 7 days at a temperature of 27C, and the
diameter of the colonies formed is then measured.
Untreated control plates are used as a reference. The
values obtained are expressed as percentages. 0 % means
no inhibitory action, 100 ~ mean~ complete inhibition of
lS growth.
Active compound~, active compound concentrations and test
results can be seen from the table below.
Le A 29 437 - 20 -
.. . . . .
";,: ~ :
. . . .
... . . .
s.~ ) J ~-
o ~
2 ~
~ o ~
2 ~ ~ ~
o ~ ~ n~ 3 n
~ 3 =n
-21 -
