Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
4~ 6
The present invention rela~es to new N,N-diethy~
N'-aryl-N'-(dichlorofluorome~hylthio)-sulPhamid~s, a ~ro-
cess for their preparation and their use in microbicidal
agents.
Fluorodichloromethylthio comPounds and their use
in plan~ protection are known from G~rman Auslegeschrif~
1,193,498. N,N-dimethyl-N'-phenyl-N'-(fluorodichloro-
methylthio)-sulphamide is described as a fungicide in
plant protection agents.
The use of N-~trihalogenomethylthio~ compounr~s for
protecting industrial mater;als against microbial degra-
dation is kno~n ~U.S. 2,553,77û~ Journ. Agr. Food Chem.
14, 365 (1966) and Fette, Seifen, Anstrichmittel ~8, 272
(1966)). However, as a result of their low solubility,
their industri3l use is not satisfactory.
- The action of N,N-dimethyl-N'-phenyl~N' (fluoro-
dichloromethylthio)-sulPhamide as microbicidal active com-
pounds in paints and plastic coatings is descri~ed in
6erman Auslegeschrift 1,Z38,139. The action of this subo
stance against fungi which damage timber is also kno~n
from "Holz als Roh- und Werkstoff 35, (1977) 233-237".
Ho~ever, this active compound is inadequate, particularly
for the protection of technical materials. For e~ample,
it is very difficult to dissolve it in the formulating
agents customary for timber protection agents, so that
large amounts of formulating agents are required in order
to apply the requ;red amount of active compound to and/or
in the timberO
The new N,N-diethyl-N'-aryl-N'-(dichlorofluoro-
methylthio)-sulphamides of the formula
e A 23 262
,. :
~2~7q~
- 2 - 23189-6042
N--so? -N-SCFC
F~1~R2
in wh,ch
R1 and R2 are identical or different and denote
hydrogen~ lower alkyl or halogen,
have been found.
As active compounds, particularly for the pro-
tection of industrial materials, the new compounds have
excellent microbicidal properties and disDlay a good solu-
bility in paints and impregnat1ng agents.
In accordance with the invention, lower alkyl
denotes, ;n general, a linear or branched hydrocarbon
radical having 1 ts about 6 carbon atoms. The following
may be mentioned specifically: methyl, ethyl, propyl, iso-
propyl, butyl, isobutyl, pentyl, isopen~yl, hexyl and iso-
hexyl. Preferred lower alkyl radicals are the methyl radi-
cal and the ethyl radical.
In accordance with the invention, halogen denotes
fluorine, chlorine, bromine and iod1ne, preferably chlorine.
ireferred new N,N-diethyl-N'-aryl-N'-~dichloro-
fluoromethylthio)-sulphamides are comDounds of the formula
C2~'5~
~ N-S02-N-SCr~C12
C2115
Rl R2
37~i
- 3 ~ 23189-60~12
in which
Rl denotes hydrogen, and
R denotes hydrogen, methyl or ethyl.
The following new N,N-diethyl-N'-aryl-N'-(dichloro-
fluoromethylthio)-sulphamides may be mentioned as examples:
N,N-diethyl-N'-phenyl-N'-(dichlorofluoromethylthio)-sulpha-
mide, N,N-diethyl-N'-(p-tolyl)-N'-(dichlorofluoromethyl-
thio)-sulphamide and N,N-diethyl-N'-(p-chlorophenyl)-N'-
(dichlorofluoromethylthio)-sulphamide.
A process for the preparation of ~he new N,N-di-
ethyl-N'-aryl-N'-(dichlorofluorometllylthio)-sulphamides has
also been found, ~hich is characterized in that substituted
sul-phamides of the formula
C2H5
N-S02-N~
C2H5 ~
1 2
R
;n ~hich
R1 and R2 have the abovementioned meaning
are reacted ~;th dichlorofluoromethanesulphenyl chloride of
the formula
ClSCClzF
in the Presence of an acid-binding agent.
The process according to the invention can be illus-
trated by means of the follo~ing equation:
C2H5~ -HCl C2H5~
NSO ~ ~ C15CC12~ - > NSO ~ CC1~F
Dichlorofluoromethan-esulphenyl chloride is known from
Ang. Chem. 76, 807 (1964).
The N,N-diethyl-N'-arylsulphamides can be prepared
in a manner which is in itself known from N,N-diethylsul-
phamyl chloricle ana aniline or 2-, 3- or 4-~oluidine or
from the corresponding halogen compounds in the presence of
an acid-~inding 3gent.
Aci~-binding agents for the process~accorcling to
the invention can be, for e~ample, alkali metal, preferably
sodium and potassium~ hydroxides and carbonates, or amines,
such as triethylamine or pyridine.
In general, customary solvents which are not
affected under the reaction conditions can be used as sol-
vents for the process according t;o the invention. Hydro-
carbons, such as toluene, chlorinated hydrocarbons, suchas chlorobenzene, ethers, such as dioxane~ or water may be
mentioned as examples~
In general, the process according to the invention
is carried out within the temperature rang~ from 0 to 100C~-
preferably fro~ 20 to 50C.
In general, the process according to the invention
is carried out under normal pressure. However, it is also
possible to carry out the process under an excess pressure
or a reduced pressure (for example within the pressure
25 range from 005 to 105 bar).
The new N,N-diethyl-N'-aryl N'-~dichlorofluoro-
methylthio)-sulphamides ran be used as active compounds
for combating microorganisms, par~icuLarly for protecting
industrial materials.
In accordance with the invention, industrial
ma~eri3ls are non living materials which have been ~repared
for use in industry~ Examples can be industrial materials
which are to be protected by active compounds according ~o
the invention against change or destruction ~y microbes,
adhesives, s;zes, paper and cardboard, textiles, leather,
tim~er, Paints and plastic articles, cooling lu~rirants
- Le A 23 262
. ~.
.
~2~ 7~i
and other materiaLs ~hich can be a~tacked or decomposed by
microorganisms~ Parts of production pLants, for example
cooling water circuits, ~hich can be impaired by the propa-
gation of microorganisms may also be mentioned within the
scope o~ the materials to be protected. Industrial
materials uhich may be mentioned preferably ~ithin the
scope of the present invention are adhesives, sizes, paper
and cardboard, leather, timber, paints, cooling lubricants
and cooling circuits. The protection of devices and/or
implements made of wood may be mentioned particularly.
Examples which may be mentioned o~ microorganisms
capable of causing degradation or change in industrial
materials are bacteria, fungi~ yeasts, algae and slime
organisms. The active compounds according to the invention
act preferentiaLly against fungi, in particular l~ould fungi,
fungi ~hich discolour and destroy timber (P3sidiomycetes~,
and against slime organisms and algae.
Microorganisms of the following genera may be men
tioned as examples:
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 Penicil~ium glaucum~
Coriolus, such as Coriolus 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~
Depending on ~he field in which it is used, an
active compound according to the invention can be converted
into the customary formulations~ suGh as solu~ions, emu~-
sions, suspensions, powders, pastes and granules.
Le A ~3 262
37~
These formulations can be prepared in a manner
wh'ich is in itself known, for examPle by mixin~ the active
compounds with a diluent consisting of liquid solvent and/or
solid carriers, if appropriate using surface-active agents,
S such as emulsifiers and /or dispersins agents, it being
possible, if necessary, to use organic solvents, such as
alcohols, as auxiliaries in the event of water being used
as the diluent.
Exa~ples of liqui-d solvents for the actiYe rom-
10 pounds can be water, alcohols, such as lower aliphaticalcohols, preferably ethanol or isopropanol, or benzyl
alcohol, ketones, such as acetone or methyl ethyl ketone,
liquid hydrocarbons, such as petroleum fractions, and
halogenated hyd^ocarbons, such as t,2-dichloroethane.
The active compounds are generally present in
microbicidal agents in an amount of 1 to 95X, preferably
10 to 75X.
The concentrations of the active co0pounds accord-
in~ to the invention for use depend on the nature and
occurrence of the microorganisms to be combated, and on
the co~position of the material to be protected. The opti~
mum amount for use can be determined by series of tests.
In general, the concentrations for use are within'the range
from 0.001 to SX 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
can also be in the form of a mixture wi~h other kno~n
active compounds. The follo~ing active compounds may be
mentioned as e~amples: benzylalcohol mono(poly~hemiformal
and other compounds which split off formaldehyde~ benzimi~
dazolyl methylcarbamates, tetramethylthiuram disulphide,
zinc salts of dialkyldithiocarbamates~ 2,4,5,6-tetrachloro--
isophthalonitrile, thiazolylbenzimidazole, mercap~o~enz-
thia~ole, organotin compounds, methylene bisthiocyanate
and phenol derivatives, such as 2-phenylphenol,
(2,2'-dihydro~y-5,5'-dichloro)-diphenylme~hane and
Le A 23 262
.
37~
3-methyl-4-chlorophenol. --
Preparation E~amples
Example 1
c2~
S02NSCC12F
' 2H; [~3
45.6 9 (0.2 mole) of N,~-diethyl-N'-phenylsulpha-
mi'de and 33.8 9 (0.2 mole) of dichlorofluoromethanesul~
phenyl chloride are ~dissolved in 2ûO ml of toluene, and
22 9 (0.22 mole) of triethylamine are added àt room tem-
perature, with cooling by water, In the course of this the
temPerature rises to approx. 35C. The toluene solution is
extracted by shaking with ~ater and is dried, and the sol-
vent is evaPorated off in vacuo. The remaining Oil (63 9)
is dissotved in methanol. Crystallisation takes place on
adding a little water. Melting point: 60 to 61C~
yield 37 9 = 51% of theory.
~reparation of the precureor
C2H5
NSO ~
55.7 9 (0.6 mole) of aniline are suspended in
200 ml of water~ 51.2 9 (0.3 mole) of N~N-diethylsulphamyl
chloride are added dropwise, with stirring~ at 40 to 50C,
the mi%ture is stirred for about 1/2 hour at this temper3-
ture, the oily reaction product is taken up in diethyl
ether, and the ethereal solution is ~ashed with aqueous
hydrochloric acid. Drying the solution and evaDorating
Le A 23 262
- 8 -
off the solvent LeaYes 40 9 of an oil. Boiling point:
200 to 205Ct10 mm, yield 33 9 = 48Z of theory.
E~a-ple 2
The compound
c2~5~
~N-So2 -NSCC12F
C2~
~
~ ~X3
is obtained in a manner analogous to that of Example 1.
Melting point: 59 to 60.
Use Examples
Example 3
10 The minimum inhibitory concentrations (MIC) of
active compounds according to the invention are deternined
in order to establish their effectiveness against fungi:
Active compounds according to the invention are
added in concentrations of 0.1 mg/l to S~000 mg/l to an
15 a~ar prepared from beer wort and peptone. After the agar
has solidified, it is contaminated witn pure cultures of
the test organisms ~isted in the Table. The MIC is deter~
mined after storage for 2 weeks at 28C and 60 to 70X
relative humidity. MIC is the lo~est conc-entration of
20 active compound at ~hich no grow~h at all by the species
of microbe used takes place; it is indicated in the Ta~e
below.
Le A 23 262
7~
.
-
CL
E
~ X
O LJ
C
._ U~ ~
C , U) O O ~ U~ o
., ~ ~ ~)
O ~
~ T
U ' ~
c
1~ ~4
U~ ~ ~
Z ~ E
:~ ~ X
O ~
U~ U~ ~ -
C
o o u~ 1~ o I
E
~ U~
C ~ o
~ . _
U~ ~ .
ul _
C .
O
~ U~
S ~ C
Ql ~
i E
C
O V~ L -- Vl C
C _ ~ O ~ ~
O ~ ~ ~ Q D ~ tO
C V) C-- O ~ _
~ ~ ~ ~ c e -- ~
v ~ ~ Y ~ ~~,
C ~-- ~-- E
-- C~J ~ 'O E i~
~ID ._ _._ ~ ~ ._
C~ ~ _ O --
L n~ E ' --
O C ~ ~ O ~ ~-
CJ ~. O ~- O ~
_ ~ ~Q~ Q~ ~ '-- '--
V~ ~CL L ~ C C
~ ~ ~ O
)- i- '~
Le A_23 262
~L2~37~i
- 10 -
Example 4 (action against slime organisms)
The active compounds according to the invention
from Examples 1 and 2, dissolved in a littLe acetone, are
used in concentrations of 0.1 to 100 mg/l in each case in
5 Allen's nutrient solution (Arch. Mikrobiol. 17, 34 to 53
(1952)), which contains 0.2 9 of ammonium chloride, 4.0 9
of sodium nitrate, 1.0 g of dipotassium hydrogen phosphate,
0.2 9 of calcium chloride, 2.05 9 of magnesium sulphate,
0.02 9 of iron chloride and 1X of caprolactam in 4 l of
sterile ~ater. Shortly beforehand, the nutrient solution
is infested ~ith slime organisms (approx~ 10S organisms/ml)
jsolated from spinning water circuits used in the prePara-
tion of polyamide. Nutrient solutions having the minimum
inhibitory concentration ~M}C) or greater concentrations
of active compound are still completely rlear after being
cultured for 3 ~eeks at room temperature, that is to say
the considerable propagation of the microbes and slime
formation which is noticeable after 3 to 4 days in nutrient
solutions free from active compound does not take place.
MIC values of 2 to 5 ~g/l are determined in this
~ay for the active compounds according to Examples 1 and 2
Example 5
Determination of the limiting toxicity values
(kg/m3 of wood) of the active compounds according to
Example 1 and 2 for Coniophora puteana and Coriolus
versicolor on pine wood and beech ~ood.
The determination of the limiting toxici~y values
is carried out by a method modelled on the method described
by H.P. Sutter~ INT. ~iodeterioration Bulletin 14 (3),
1978, pages 95 to 99.
FreshLy cut thin pieces of end grained ~ood (dimen-
sions 40 x ~0 mm, thickness about 2 mm~ are each impreg-
nated in vacuo with solutions of differing concentrations
of active comPound for the tests. The amo~n~ of active
compound absorbed in kg/m3 of wood is determined from the
retent;on of solution (which is determined by weighing the
Le A 23 262
~2~7~6
samples before and after impregnation), the
density of the wood and the concentration of ~he active
compound in the impregnation solution used.
Of the 15 dry test specimens per one active com-
pound concentration, 5 test specimens are exposed to fungalattack without any treatment, 5 further specimens are sub-
jected to treatment in a wind tunnel (~ind velocity: 1 ~
0.1 mlsec; temperature: 40 ~ 2C) for ~ weeks, and 5 other
test specimens are subjected to a water soakin~ treatment
modelled on DIN EN 84 (storage for 14 days in distilled water
at 20C; water changed 9 times).
For the mycological test, the test specimens are
sterilised with propylene oxide and then pLaced individually
on the fully develoPed mycelium of the test fungus on malt
extract agar in a Petri dish, the distance between agar sur-
face and specimen being kept at about S mm by ~ans of spacers.
After storage for 6 ~eeks at 21-23C, the degree of destruc-
tion of the test specimen is determined visually.
The two concentrations of the active compound, in kg/
m3 of wood, at which the wood is still just attacked and at
which it is no Longer attacked 3re determined as the limiting
values of the toxic action.
The average toxicity limits for the substances accor-
ding to the invention from Example 1 and 2 and for the known
active compound dichlofluanide are shown ;n the Table which
follo~s~ for t~o test fungi and two different types of
wood.
Mean toxicity Limits (kg/m3 of wood) for active com-
pounds from Example 1 and 2, for wood-destroying fungi.
Le A 23 262
~z~ 6
- 12 -
o
o ~oc I~ U~
~ L r~l ~)
l~J
,~
L
o
01
O C
c~ ~_ L~--
o ~
~ m
L ~n~ O
a) ~ ,u :~u
~ ~ Y
L ~ C .
O L ~~It
O ~E~
O ~ `OU~
S f~ .
_ ~ ~ O
U) O _ L
o ~
E O
O O C
U 3 0
._
t_ ~ O
. '
L
Q ~ 3
~ ~05
O C
O ~ t~ C
aJ L L _
C 00
O ~ ~ ~ ~
O L Q ~ n~ O O N
o ~ el 3(1
3U~ t~
L ~
O C
O ~ ~ ~)
~ Q ~ E
E ~ ---- ~ ~:r 1~ O`
-- C ~ 3~ O O -
a~ 3 0 -
., ~ 3
_-, .
E
._
O --~
t_)
C~
1 .
X;I~ ~: T ~ ' . ,_ . .
4 . O
. O
Z ._
1-
L P ~ U~
T :1: ~ .,
:~ X C~ ~ ~J
~ ~ _ 3:
Le A 23 262
._ _ . . .
,
~2~87~
~ 13 -
Examole 6
The solubili.ties of active compounds according to
the invention from Example 1 and 2 compared with dichlo-
fluanide, commercially availa~le, in organic solvents for
wood preserva~ives.
Active compound Solubility (~) in:
White spirit Shellsol A8
16 71
(C2HS~2N S02 N S CCl2F
'~1
(C2~I5) 2N-S02-N-S-CC12P
W 59 67
(CH3) 2N-502-N-S~ 2F
~ 0.7 6
tdichlofluanide)
(White spirit and Shellsol AB are commercially available
lo~l-boiling hydrocarbons).
~ ~ k
Le A 23 2S2
