Note: Descriptions are shown in the official language in which they were submitted.
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Fungicides for the protection of materials
'~he invention relates to the use oE 1-iodo-1-alkynols as
fungicides for the protection of industrial materials.
1-Halogeno-1-pro~en 3-ols and their use for combating
~hytophtora infestans and Venturia species are known from European
Patent 0,002,679. ~oreover, they can be used for combating cereal
diseases such as grain rust and stinking smut of wheat.
Surprisingly, it has been shown that a number of 1-iodo-
1-alkynols are particularly suitable for the protection of indus-
trial materials. ~iicrobicidal agents have therefore been found
which contain 1-iodo-1-alkynols of the Eormula
~ X~l 2
I - C - C - (C~I2)n
in which
X1, x2 and X3 are identical or different and denote
hydrogen, fluorine, chlorine or bromine,
n represents the numbers 0 or 1 and
R1 denotes lower alkyl, cycloalkyl, halogen-substituted
lower alkyl, aralkyl optionally substituted by halogen,
lower alkyl, halogenoalkyL, lower alkoxy, lower
halogenoalkoxy or phenyl, or aryloxyalkyl, optionally
substitut:ed by halogen lower alKyl, halogenoalkyl, lower
alkoxy, lower halogenoalkoxy or phenyl.
According to the invention, lower alkyl generally
denotes a straight-chain or branched hydrocarbon radical having 1
to about 6, preferably having 1 to 4, carbon atoms. Examples
which may be mentioned are: methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
~ccording to the invention, cycloal~yl generally denotes
a cyclic hydrocarbon radical having 3 to 7~ preferably 5 or 6,
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carbon atoms. Examples which may be mentioned are: cyclopropyl,
cyclobutyl r cyclopentyl, cyclohexyl and cycloheptyl.
According to the invention, halogen-substituted lower
alkyl generally denotes a straight-chain or branched hydrocarbon
radical having about 1 to 6, preferably 1 to 4, carbon atoms and
substituted by i to 5, preferably l to 3, fluorine, chlorine,
bromine or iodine atoms. Examples which may be mentioned are:
trifluoromethyl, trichloromethyl, diEluoro-chloromethyl and
1~ fluoro-dichloromethyl.
According to the 1nvention, aralkyl generally denotes a
hydrocarbon radical having 1 to about 6, preferably l to 4, carbon
atoms and substituted by 1 to 3, preferably one, aryl radical,
preferably a phenyl radical. Examples which may be mentioned are:
benzyl, ~-chlorobenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl,
2,6-dichlorobenzyl, 4-fluorobenzyl, ~-methoxybenzyl, 4-methyl-
benzyl and 2-chloro-4-methylbenzyl.
According to the invention, aryloxyalkyl generally
denotes a hydrocarbon radical having 1 to about 6, preferably 1 to
4, carbon atoms and substituted by 1 to 3, preferably one, aryloxy
radical, preEerably a phenoxy radical. Examples which may be
mentioned are: phenoxymethyl, 4-chlorophenoxymethyl, 3,4-
dichlorophenoxymethyl, 2,4-dichlorophenoxymethyl, 4-fluorophenoxy-
methyl and 2,6-dichlorophenoxymethyl.
The aryl part of the aralkyl radicals and aryloxyalkyl
radicals can optionally be :Eurther substituted by other customary
radicals. Examples which may be mentioned are: ha:Logen, prefer-
ably fluorine, chlorine or bromine, lower alkyl, preEerably
methyl, ethyl, propyl and isopropyL, lower aLkoxy, halogenoalkyl,
preferably methyl or ethyl which is substituted by 1 to 3 halogen
atoms, preferably ~luorine or chlorine, in particular trifluoro-
me~hyl, trichloromethyl, di~luoro-chloromethyl, fluoro-
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dichloromethyl, ~ trifluoromethyl. and ~-trichloroethyl,
halogenoalkoxy, preferably methoxy or ethoxy which is
substituted by 1 to 3 halogen atoms, preferably fluorine
or chlorine, particularly preferably trifluoromethoxy
and trichloromethoxy, and phenyl.
The aryl part can generally be substituted by 1
to 3 other radicals.
Preferred microbicidal agents, according to the
invention, for the protection of industrial materials
contain 1-iodo-1-alkynols of the formula
OH Xl (II)
I - C _ C - (C~2) - C ~ ~X3
in which
Xl, x2 and X3 have the abovementioned meaning
and
R2 denotes an alkyl radical having 1 to 6 carbon
atoms, a cycloalkyl radical having 3 to 7 carbon
atoms, a straight-chain or branched hydrocarbon
radica:l having 1 to about 6 carbon atoms and
substituted by 1 to 5 halogen a-toms, an aralkyl
radica.L having 1 to about 6 carbon atoms in the
alkyl part and optionally substituted in the aryl
part, or an aryloxyalkyl radical having 1 to
about 6 carbon atoms in the alkyl part and op-
tional:ly substituted in the aryl part.
Specifically, the preferred microbicidal agents,
according to the invention, for the protection of indus-
trial materials are those which contain l-iodo-l-alkynols
of the formula
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. . _
-- 4 --
X
I - C _ C - (C~ ) - C ~ X (III)
2 n
in which
xl has the abovementioned meaning,
X4 denotes hydrogen, fluorine or chlorine,
X5 denotes hydrogen or chlorine and
R3 represents methyl 9 ethyl, isopropyl, tert.-
butyl or cyclohexyl.
The 1-iodo-1-alkynols according to the invention
can be prepared by treating the corresponding l-pro--
10 pynols with iodine in the presence of an aqueous alkali
metal hydroxide solution and, if appropriate, in the
presence of a diluent.
Incorporation of the active compounds according
to the invention into materials which are exposed to
15` attack by fungi and bacteria inhibits the growth of the
fungi and bacteria; the origin~l value o~ the materials
is thus retained. The compounds are involatile,
water-insoluble, insensitive to light and heat-stable,
so that they are stable in such materials for prolonged
20 periods of time.
~ ithin the scope of the present invention, indus-
trial materials are products which do not themselves
occur in nature, but are produced from natural or syn-
thetic starting materials. Within the scope of the pre-
25 sent invention, the products to be protected are indus-
trial mater;als which can ke decomposed by micro-
organisms.These industrial materials include non-living things,
especially semi-products or intermediate for final articles.
E~amples of industrial materials which are in~
30 tended to be protected, by the substances according to
the invention, from microbial modification and destruc-
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tion are adhesives, glues, papers and cardboards, tex-
tiles, leather, wood, coating agents, plasters, cooling
lubricants and plastic articles which can be attacked
and decomposed by microorganisms. In the context o~
the materials to be protected, parts of production in-
stallations, such as, for example, cooling water cir-
cuits and cooling lubricant circuits, the operating capa-
bility of which can be impaired by microorganisms, may
also be mentioned. Preferably, the active compounds
10 according to the invention can be used for the protection
of adhesives, paper, cardboard, coating films, wood and
the like.
Examples of microorganisms which can cause degra-
dation or modification of industrial materials are bac-
15 teria, fungi, yeasts, algae and slimes. Pre-
ferably, the substances according to the inverition are
active against fungi dnd bacteria3 fungicidal action in-
cludes mould fungi and also fungi which destroy and dis-
colour wood.
Microorganisms of the following families may be
mentioned by way of examples: Escherichia, such as Esche-
richia coli, Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus, Alternaria,
such as Alternaria tenuis, Aspergillus, such as Aspergil-
25 lus niger, Chaetomium, such as Chaetomium globosum, Conio-
phora, such as Coniophora cerebella, Lentinus, such as
Lentinus tigrinus, Penici]lium, such as Penicillium glau-
cum, Polyporus, such as Polyporus versicolor, Pullularia,
such as Pullularia pullulans, Scleroph~oma, such as Sclero-
30 phoma pityophila~and Trichoderma, such as Trichodermaviride.
Depending on their field of application, the sub-
stances according to the invention can be converted to the
customary formulations such as solutions, emulsions, sus-
-35 pensions, powders, pastes and granules. These can be
prepared in a manner which is in itself known, for example
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by mixing the active compounds with an extender which con-
sists of liquid solvent and/or solid carriers, if appro-
priate using surface-active agents such as emulsifiers
and/or dispersing agents, it being possible, if appro
priate, to use Grganic solvents as auxiliary solvents, for
e~ample in the case where extenders are used.
Examples of organic solvents for the active com-
pounds can be alcohols, such as lower alcohols, preferably
ethanol or isopropanol, or benzyl alcohol, ketones, such
as acetone or methyl ethyl ketone, liqu d hydrocarbons~
such as benzine fractions, and chlorinated hydrocarbons,
such as 1,2-dichloroethane.
The microbicidal agents according to the inventio.
generally contain 10 to ~G0% by weight, pre~`erably 50 to
80% by weight, of the l-iodo-l-alkynols as the active
compound.
The use concentration of the substances according
to the invention depends on the type and the occurrence of
the microorganisms to be comb..ted, and also on the com-
20 position of the material to be protected. The optimul,
amount to be used can be determlned by series of tests.
The use concentrations are generally in the range from
0.001 to 5% by weight, preferably from 0.05 to 0.5% by
weight, relative to the material to be protected.
The new active compounds according to the inven-
tion can also be present in a mixture with other known
active compounds. The following active compounds may
be mentioned by way of examples: benzimidazolyl me-thylcar-
bamate, tetramethyl-thiuram disulphide, N-fluorodichloro-
30 methylthio-phthalimide and N,N-dimethyl-N'-phenyl-(N'-
fluorodich].oromethyl.thio)-sulphamide, compounds which
spl.it off formaldehyde, such as hemiformals, oxazolidines,
hexahydro-s-triazines, N-methylolamides, and phenol deri-
vatives, such as p-chloro-m-creso]., 2-phenyl-phenol and
(2,2'-dihydroxy~5~5'-dichloro)-diphenylmethane.
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Preparation examples
Example 1
OH
I - C _ C - C .~3Cl
CH3
266.5 g (1.05 mols) of iodine are introduced in
portions into a solution of 180.6 (1 mol) of 3-(4-chloro-
phenyl)-l-butyn-3-ol in 2,000 ml of methanol, at 10 to
15C, and 400 ml of concentrated sodium hydroxide solution
are simultaneously added dropwise during this introduction.
After three hours, the reaction mixture is stirred into
10 2 litres of water and the oil which has separated out is
taken up in 500 ml of ethyl acetate. The ethyl acetate
phase is washed with three times 50 ml of water, dried
over anhydrous sodium sulphate and then e~aporated under
reduced pressure. The residual oil crystallizes on
15 trituration with a small amount of petroleum ether.
This yields 230 g (75% of theory) of 1-iodo-3-(4-chloro-
phenyl)-l-butyn-3-ol as co]ourless crystals with a mel-
ting point of 84 to 85C.
Example 2
OH
20 I - ~ - C - CH2 - C ~ Ci
r~ 3
144 ml of concentrated sodium hydroxide solution
are added dropwise to a solution of 58.4 g (0.3 mol) of
4-(4-chlorophenyl)~1-pentyn-4-ol in 600 ml of methanol,
at 20 to 25C and with slight external cooling, and
25 91.5 g (0.36 mol) of iodine are introduced simultaneously
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in portions during the dropwise addition, After 8
hours, the reaction mixture is stirred into 1.5 litres of
water. Extraction is carried out with twice 250 ml of
ethyl acetate, the organic phase is washed with water and
the solvent is distilled off under reduced pressureO
This yields 85 g (88.4% of theory) of :L-iodo-4-(4-chloro-
phenyl)-l-pentyn-4-ol as a weakly yellowish-coloured oil
with a refractive index n20: 1.6078.
The following examples of the general formula (I)
xl
OH j 2
I C ~ C - (CH2) - C ~ (I)
I1 ~ X3
are obtained in a corresponding manner.
- Example 1 2 3 ~ Physical constants
l~ No. n X X X R (melting point C;20
refractive index nD
13 0 4-Cl '-Cl H 3 72 to 74
4 0 H H CH3 1.5661
0 4-Cl H H iso-C3-H7 1.593
6 0 4-F H H iso-C3-H7 57 to 59
7 1 4-C1 3-Cl H CH3 1.6107
8 1 4-F H H CH3 1.5781
9 1 4-Br H H CH3 1,622
1 H H H iSo-C3-H7 1.5839
11 1 4-C1 H H iSo~c3-H7 1,5878
12 1 A-Cl ~. c2~s 1,S7~2
13 1 a~F H H iso-C3-H7 1,5668
1~ 1 d-Cl 2-Cl H .c2~5 1.6039
1 4-C1 2-C1 H CH3 1.6148
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~ . . . _
~.~.B~
Physical constants
Example 1 2 3 (melting point C;20
No. n X X X R refractive index nD )
16 1 4-F H H ~ 1,5771
17 1 H H H ~ 1.5912
18 1 4-F H H c2;~5 1.5702
19 1 H H H C2H5 1,5908
1 4-C1 3-Cl H C2H5 1.6060
lO 21 1 H ~ ~ - c~3 1.6017
Application examples:
Example 22: Action against fungi
The compounds according to the invention were in-
~5 corporated, in graded concentrations of between 1 and5,000 mg/litre of test sample, into an agar which had been
prepared from beer wort and peptone. After solidifi-
cation of the agar, the agar samples prepared in this way
were contaminated with pure cultures of various test fungi
20 (see table).
After storage for two weeks at 28C and 60 to 70%
relative atmospheric humidity, an evaluation was made.
In the table, the smalles-t concentration of the substance,
contained in an agar sample, at which there was no growth
25 at all of the species used is given as the minimum inhibi-
tory concentration (MIC).
In this test, the following compounds, for ex-
ample, show a very good action: compounds according to
Preparation Examples 1 and 2.
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-- 10 --
~3PFIF~ a~oT~Fl,I, o o
FnU~ ~F~ul~
c~ o
um~n~l~ umFT ll~-U~a u~ o
~ o o
~:: ulnsoqol5 ulnFul0~ :f~ o
o o
~o
~51u snllF~3ds~ ~
o
~ ~I0l02FSla~ snlod~loa
,~ ~
F~ ~ I F~do~ F d YuIo~dol a 1~ S
.~su~inllnd ~ nllna O o
~ m
¢snuF15F~, snuF~u~rI o
~n
q~l~o ~lo~doFuo;) o
.
sal~ds ~UFMOT10,~ a~ c
,~ UI Ul anl~ I
~ ~3 o--~
o~
o c
A I ~ O O H _ ~ ~
? ~
.
-- 1 ]
Example 23
Action against bacteria
An agar which contains bouillon as -the nutrient
medium is treated with the active compounds according to
the invention in concentrations o~ 1 to 5,000 ppm. The
nutrient medium is then infested in each case with
Escherichia coli or Staphylococcus aureus and the in~es-
ted medium is kept for 2 weeks at 28C and 60 to 70%
relative atmospheric humidity. The MIC is the lowest
concentration of active compound at which there is no
growth at all of the microbial species used.
In this test, the compounds according to Pre-
paration Examples 1 and 2 are used:
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... . _
- ~
~,~
h
~1
~ ~0
:: ~ ~
naln~ o
c:sn~o~ol~d~?~S
o
E
C' Fl~ en~F~a~s~
c~
¢
u
O-u~
~ o c~
O I ~ U
-
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