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Патент USA US2408260

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Patented Sept.v24, 1946
2,408,259
UNITED ,"STATE SVIPATENT, OFFICE2,408,259‘
‘
VAT DYESTUFFS A121) PROCESS OF MAKING
Theodor Holbro, Basel, Walter'Kern, Sissach‘, and
Paul Sutter, Basel, Switzerland, ass’ignors to-So
ciety of Chemical Industry in Basic, Basel,
Switzerland
No Drawing. Application February 4, 1943, Se
,rial No. 474,728.
In Switzerland ' January 8,
1942
(01. 2604303)
13 Claims.
2
The present invention is concerned with new
vat dyestuffs and a process for producing the
same. More particularly the invention is con
cerned with vat dyestuffs of the anthraquinone
ill-position of the anthraquinonc nucleus are in
volved in ring formation. The reaction may
be carried out symmetrically in 1:9 and .5:10‘or
in 1:9 and 4:10 positions, or according to the
circumstances‘?rst one ring and. afterwards a
series and still more particularly with those con
taining carbonamide groupings and/or hetero
cyclic groupings derivable “therefrom.
‘ second ringfmay be closed, whereby asymmetrical
A considerable number of vat dyestuffs con
Amongst, heterocyclic rings which may ' be
anthraquinone derivatives may be obtained...“ '
taining carbonamide groupings is already known.‘
fused on according to. methods knownper se
Amongst this group. of vat dyestu?s, generally 10 there are six-membered rings. such as pyridine,
speaking, those are of special interest which dye
‘ pyridone, pyridazinapyrimidine and pyrimidone
yellow tints because yellow'andmore particu-v
larly bright yellow to greenish yellow tints are
not easily obtainable with vat dyestuffs of other
rings which may carry substituents such as alkyl
groups, especially lowerialkyl' groups containing
groups. However it is generally known that I
many yellow to greenish yellow vat dyestuffs are
defective in fastness to light and/or af?nity to
cellulosic ?ber and therefore there is still a
strong demand for better'dyestuffs.
1 :5-dichl0ranthraquinone-2 : G-dicarboxylic , acid
According to the present invention new and
can be-transformed by direct reaction with'alkali
polysul?des such as sodium disul?de and am
valuable vat dyestuffs'are prepared by reacting
carboxylic acids of anthraquinone derivatives,
containing at least two rings, at least cne'of
which is heterocyclic, linked to at least‘two'peri
monia i-nto ,, 1-:9,5; l0.-anthradithiazol-2,6-dicar
boxylic acid, or the‘same product may be con
densed with alkyl-hydrazines,- such as methyl
‘positions of the anthraquinone nucleus, with
amines of vattable compounds.
up to?vecarbon atoms or carboxylic groups.
Insome cases ?ve-membered rings are of espe
cially favorable. character'such as thiazole and
‘pyrazole rings which may also carry substite
uents as mentioned above. By way .of example
l
hydrazine
I
The starting compounds ‘required for the
present process viz. anthra'quinone‘ compounds
with heterocyclic rings linked to'pperi-positions
may be prepared from such anthraquinone sub
stitution products containing substituents‘ in at
least two ‘alpha-positions which promote ring
formation; e. g. halogen, amino, hydroxyl nitro,
or carboxylic groups.’ Besides these substituents
to . 1:9,5z10-di-(N)-methy1-pyrazol
,anthrone. .For the preparation of other anthra
quinone derivatives containing heterocyclic rings
other. methods and conditions are necessary,
which are-known, per se and only theirapplica
.30 tionisto be-adapted to the special case.
7 " If these anthraquinonederivatives containing
heterocyclic rings do not yet possessthe desired
carboxylic groups or functional derivatives there
of, such groups may be introduced into the mole
required forring formation the said anthra V35 cule in a separate step, for example by exchange
quinone substitution products may contain fur-v
or transformation of substituents already present
ther' substituents preferably ‘of such nature
and/or in such positionsthat'they do‘ not inter
fere with the intended formation 'of rings.
Amongst such additional substituents carboxylic
or purposely introduced, for or into carboxylic
groups.
I
,
v
‘
’
~
As already. mentioned new vat dyestuffs are
made from these anthraquinone derivatives con
groups and/or substituents or groupings capable ‘
tainingasv substituents one, preferably two, or
of being‘transformed into or of being replaced
more .carboxylic groups and having fused ‘on at
by carboxylic groups or functional‘ derivatives
least-gtwowrings in peri-positions, which rings
thereof are to be mentioned. As _there are four
may be, .of- the same or of different kind and at
combinations‘ of peri-positions in the anthra .45 least'on'e of .the said ringslbeing ‘heterocyclic and
quinone nucleus (1:9, 8:9, 4:10, 5:-l0)pto which ' therefore containing one ‘or more hetero-atoms,
rings can be linked, the substituents intended for
‘for; examplenitrogen, sulfur and oxygen alone
ring formation can be‘ in any two or more than
or in combination. The carboxylic groupsnmay
two of the four alpha-positions, for example :in
be situated in’th'e anthraquinone nucleus or in
1 and 4 or preferably in 1 and 5 (or 4 and'8 re
spectively) position whereas it ispreferable, but
.50 a. hetero. ring., Some especially valuable dye
stuffs are obtained from anthradithiazole car
not necessary, that additional substitution oc
cupy beta-positions, for example 2 and 7 or pref
erably 2 and 6 position if two additionalsub.
stituents are present,or only one of ‘these posi: 55
tions or even more.
'
For the preparation of the present starting
compounds atleast two rings (one atfleast be
ing heterocyclic) are linkedyto at least two peri
positions whereby preferably both the _9- and‘ the
boxylic acids. such as 1:9,5;IO-anthradithiazole
2:6-(or 4:8)-dicarboxylic acid or from the cor
responding mono-carboxylic acids, containing
only one carboxylic group, for example in 2
position.
A
'
The new vat dyestuffs are made by reacting
ftheisaid carboxylic acids with vattable com
pounds containing amino groups. vattable com
poundssuitable for this purpose are those for
2,408,259
'
3
4
The present invention provides inter alia yellow
example which belong to the anthra'quinone se
dyestuffs of very pure shade possessing very good
all-around fastness and especially excellent fast
ries. They may be aminoanthraquinones or may
contain condensed ring systems containing more
ness to light.
than three six-membered carbon rings, such as
,
It is interesting to note that practically all car
aminodibenzanthrones and aminopyranthrones,
boxylic acids hitherto used for preparing vat dye
stuffs of the carbonamide type if combined with
or such as are obtained by condensing hetero
cyclic rings with an anthraquinone nucleus, as
,Z-aminoanthraquinone yield dyestuffs of such
aminoanthrapyrimidines or aminoanthraquinone
inferior strength and af?nity for cellulosic ?bers,
enzacridones.
Amongst the aminoanthra
quinones l-aminoanthraquinone and 2-amino 10 that these dyestu?s are devoid of any value. In
contradistinction to this the present dyestu?s in
anthraquinone may be mentioned and especially
which Z-amino-anthraquinone is present as com
aminoanthraquinones containing further subs
ponent show good affinity and strength. As com
tituents such as alkoxy (methoxy) or acylamino
pared with the corresponding dyestu?s made
groups, wherein the acyl residue may be derived
from l:5-anthraquinonedicarboxylic acids and
15
from an aliphatic (e. g. acetic) aromatic (e. g.
vattable amines the dyestuffs of the present in
benzoic and substituted benzoic) or heterocyclic
vention are quite generally distinguished by much
(e. g. pyridinecarboxylic) acid, and halogen
improved affinity and fastness to light and
atoms such asychlorine or bromine.
strength.
This list of compounds is not limitative but
The following examples illustrate the invention
only illustrates the invention. Further vattable 20 but are not intended to limit it in any way, the
amino-compounds not belonging to the anthra
parts being by weight:
quinone series may be used, such as amino-sub
stitution products of indigo, thioindigo, pyrene
Example 1
quinone, dibenzpyrenequinone as well as similar
13 parts of 1:9.5:l0-anthradithiazole-2:6-di
compounds, There too substituents as are per 25
carboxylic acid chloride of the formula
missible in vat dyestuffs may be present.
In several instances such vattable compounds
may be used which, for instance in ortho-posi
tion to an amino group, contain at least one sub
stituent which gives rise to formation of a hetero
30
cyclic ring. Such substituents are for instance
the hydroXyl-, mercapto-, nitro- or amino
groups as well as halogen atoms. According to
the particular conditions oxazole-, thiazole- and
imidazol-rings may be formed immediately fol 35 and 800 parts of dry ortho-dichlorobenzene are
lowing the reaction with the carboxylic acids or
heated to 150-160“ C. while stirring and mixed at
this temperature with a hot solution of 23 parts
their functional derivatives, or these rings may
of 1-amino-5-benzoylaminoanthraquinone in 400
be formed in a separate step, according to gen
erally known methods.
parts of ortho-dichlorobenzene. The formation
For carrying out the reaction with vattable 40 of dyestuff is complete after 2 hours’ stirring at
compounds containing amino groups, the car
the boil. The crystallized dyestu? is suction-?l
boxylic acids mentioned above are used prefer
tered in the heat, Washed with ortho-dichloro
benzene and alcohol and dried. The dyestuff
ably in form of their functional derivatives, ca;
which is obtained in very good yield is a yellow
pable of reaction, i. e. as acid halides or acid
amides. The reaction may be carried out in in 45 powder dissolving in concentrated sulfuric acid
different dispersing or dissolving agents, partic
to a red solution and dyeing cotton from a yel
ularly those having a high boiling point, such as
low-olive vat strong reddish yellow tints having
very good fastness properties.
chlorobenzene, dichlorobenzenes, or nitrobenzene,
When substituting l-amino-ll-benzoylaminow
at elevated temperatures for instance at the
boiling point of such indifferent solvents. In cer 50 anthraquinone for the l-amino-5-benzoylamino
anthraquinone there is obtained a red powder by
tain instances room temperature or a slightly
the same method of working which dissolves in
raised temperature may be more suitable. Ac
cording to known methods agents capable of bind
concentrated sulfuric acid to a red solution and
dyes cotton from a yellow-olive vat red-orange
ing acid, agents capable of eliminating ammonia
or catalytically active agents may be used. The 65 tints having good fastness properties.
The 1 : 9,5 : 10-anthradithiazole-2 : G-dicarboxylic
addition of tertiary bases such as pyridine to the
acid chloride used in this example has been pre
reaction medium has proved to be of particular
advantage in many instances. Ifdichlorides of
pared as follows:
dicarboxylic acids are used the proportions of the >__._
reagents are preferably so chosen that all the
carboxylic acid groups enter into reaction.
The products of the present invention may also
be obtained in a somewhat different way by re
16b
acting the corresponding carboxylic acid amides ,
with vattable compounds containing an ex
changeable halogen atom.
l8.2-5 parts of 1:5-dichloroanthraquinone-2:6
dicarboXylic acid, 16.5 parts of sulfur, 110 parts
of crystallized sodium sul?de and~290 parts of
ammonia of 12 per cent strength are heated in
an autoclave provided with a stirrer for 8 hours
to 95-105“ C. When cold the content of the
autoclave is suction-?ltered, the ?lter residue is
dissolved in 600 parts of boiling water, the solu
tion is ?ltered and the disodium salt of the
The products of the present invention are vat
l : 9,5: IO-anthradithiaZole-Z : S-dicarboxylic acid
dyestu?s and may be used accordingly for dyeing
is salted out from the ?ltrate with common salt.
and printing the most diverse ?bers of animal or
vegetable origin, such as wool, silk and leather, 70 It is suction-?ltered, washed with a saturated
solution of common salt, the ?lter cake is boiled
but especially cotton, hemp, rayon and staple
?bers from regenerated cellulose as well as mix
tures of the aforementioned ?bers. They may
further be converted according to known meth
ods into leuco sulfuric acid esters.
with water with addition of some animal charcoal,
the solution is ?ltered and the 129,5:10-anthra
dithiazole-Z:G-dicarboxylic acid is precipitated
75 from the ?ltrate with hydrochloric acid.
After
24085259
5
?ltering, washing and drying a, yellow-green
crystalline powder is obtained in good‘yield which
does not melt below 450° C.
_ >
11.8 parts of 1:9,5:IO-anthradithiazdle-Z:6-Cli
,
6
.
a
1 '(N) -2-benzacridone 4-.amino-1': Q-anthrapyrim
idine'there is obtained a yellow-brown powder
which dyes cotton from a yellow-olive vat yellow
shades.
carboxylic acid are heated to boiling during 1 5
'
Example 4
hour with 12 parts of thionylchloride and ‘530
19.5 parts of 1:9,5:IO-anthradithiazole-Z:6-di
parts of dry ortho-dichlorobenzene. After dis
carboxylic acid chloride are heated to 150~160° C.
tilling 65 parts of the mixture--the unconsumed
thionylchloride being thereby removed—it is suc
with 1300 parts of dry trichlorobenzene, while
tion-?ltered while hot and the ?ltrate is allowed 10 stirring. and mixed at this temperature with a’
hot solution of 25.5 parts of l-mercapto-2-amino
to cool. The 1:9,5:lo-anthradithiazolea:6-di
anthraq-uinone in 650'parts of trichlorobenzene.
carboxylic acid chloride crystallizes in greenish
The splitting off of hydrochloric acid and water
yellow laminae melting at 323-325° C. after ?l
tering, washing and drying.
is complete’ after stirring for 2 hours. The pre
cipitated dyestuff is suction-?ltered in the heat,
Example 2
Washed with trichlorobenzene and alcohol and
dried. A :brown powder is thus obtained which
13 parts of 159,5:10-anthraditlnazole-2:6~di
carboxylic acid chloride and '800 parts of dry
dissolves in concentrated sulfuric acid 'to a red
solution and dyes cotton from a yellow-olive vat
ortho-dichlorobenzene are heated to 150-160° C. 20 orange-brown shades.
while stirring and mixed at this temperature with
The dyestuffs .can be puri?ed as‘ follows:
a hot solution of 14.9 parts of a-amino-anthra
2.5 parts of dyestuf.F powder are dissolved in 50
quinone in 400 parts of ortho-dichlorobenzene and
parts of concentrated sulfuric acid.- This solu
10 parts of pyridine. The formation of dyestu?
tion is poured onto ice, the precipitated dyestuff
is complete after stirring for 2' hours at the boil.
is suction-?ltered, washed with water and sus
The precipitated dyestuif is suction-?ltered in the
pended in 200 parts of water. 40 par-ts of sodium
heat, washed with ortho-dichlorobenzene and
hypochlorite solution of 14 per cent. strength are
alcohol and dried. The dyestu? so obtained is a
added and stirring is continued for 1/2 hour at
yellow powder dissolving in concentrated sulfuric
boiling temperature. The dyestuff thus becomes
acid with a red solution and dyeing cotton from a
orange-"red. It is suction-?ltered, washed and
yellow-olive vat strong yellow tints.
dried. It dyes cotton orange-brown shades of
When using the equivalent quantity of l-amino
greater purity than the crude product.
G-chloranthraquinone or I-amino-5-methoxy
anthraquinone instead of m-aminoanthraquinone,
there are obtained dyestuffs which dye cotton from
The dyestuif has probably the following con
stitution:
.
‘
a yellow-olive vat also yellow tints.
When substituting ?-aminoanthraquinone for
the u-aminoanthraquinone there is obtained a
greenish yellow powder which dissolves in concen
trated sulfuric acid to a red solution and dyes cot
ton from an orange-brown vat strong greenish 40
yellow tints.
Example 3
13 parts of 1:9,5:IO-anthradithiazole-Z:6-di
carboxylic acid chloride and J700 parts of dry
7 Example 5
nitroberrzene are heated whilestirring to ‘ISO-160°
C. and mixed at this temperature with a hot
13 parts of 4: l0;8:9-anthradithiazole-l:5-di
solution of 22.7 grams of 4-aminoanthraquinone
1(N) :Z-IbenZacridQne in 700 parts of nitrobenzene 50
and 10 parts of pyridine. The precipitated dye
stuff is suction-?ltered after two hours’ .stirring
at boiling temperature, washed with nitro-ben
zene and alcohol and dried.
carboxylic acid chloride of the formula
It is a dark olive
powder of the formula
55
C10
and. 800 parts of dry ortho-dichlorobenzene are
heated to 150—160° C. while stirring and mixed at
this temperature with a hot solution of 23 parts of
l - amino-5-fbenzoylaminoanthraquinone in 400
parts ‘of ortho-dichlorobenzene. The formation
of .dyestuif is complete after stirring for 2 hours
at ISO-160° C. The dyestuff is suction-?ltered
in the heat, the residue is washed with ortho
dichlorobenzene and alcohol and dried. The dye
stuff which is obtained in very good yield is a yel
low powder dissolving in .concentrated sulfuric
acid to a. red solution and dyeing cotton from
70
dissolving in concentrated sulfuric acid to a red
solution and dyeing cotton from an olive-brown
vat olive shades.
'
When using instead of 4-aminoanthraquinone
a red-brown vat yellow shades.
When substituting 1-amino-4-rbenzoylaminoan
thraquinone for the 1-amino-5-benzoylaminoan
thraquinone there is obtained a red powder dis
solving in concentrated sulfuric acid to a red so
lution and dyeing cotton from a violet-brown
vat red-orange shades. ,
.
2,408,259
7
8
zoylaminoanthraquinone, as described in Efrain
When using the equivalent quantity of 1- or 2~
amino-anthraquinone instead of l-aminoe5
benzoylamino~anthraquinonc there are obtained
dyestu?s dyeing cotton more greenish shades.
ple 5. The dyestuii obtained is a brown powder
dissolving in concentrated sulfuric acid to a red
solution and dyeing cotton from an olive-brown
vat yellow-brown shades.
The 4:19,8:9-anthradithiazole - 1:5 - dicarbox
When substituting l—amino-5~benzoylarnino
ylic acid chloride used in this example has been
anthraquinone for the l-amino-a-benzoylamino
anthraquinone there is obtained a brown powder
prepared in analogous manner like the above de
scribed 1:9,5:10~anthradithiazole-2:6 - dicarboX
dissolving in sulfuric acid to a red-brown solu~
ylic acid chloride from 4:8-dichloroanthraqui
none-1:5-dicarboxylic acid. From dichlerobem 10 tion and dyeing cotton from an olive-brown vat
brownish yellow shades.
zene it is obtained in ?uorescent greenish yel
Example 8
low needles.
The 4:10,8:9-anthradithiazole
l:5~dicarboxylic acid formed as intermediate
1 ‘part of the dyestuff obtained according to
product is a yellow-green powder melting at 370°
Example 1 (cf. paragraph 1) is suspended in 100
C. with decomposition.
parts of water with addition of 4 parts by volume
of caustic soda solution of 36° Bé. and the sus
Example 6
pension is vatted with 2 parts of sodium hydro
13 parts of di-(N)—rnethyl-1:9;5:iO-anthra~
dipyraoole-Z16-dicarboXylic acid chloride of the
sul?te at about 50° C. This stock vat is added
to
a dye-bath which contains 3 parts by volume
20
of caustic soda solution of 36° Bé.‘ as well as 1
part of sodium hydrosul?te in 2000 parts of
water. 100 parts of cotton are entered at 40° C.,
25
30 parts of common salt are added after 15 min
utes and dyeing is continued at ail-45° C. for
further 415 minutes. The cotton-is squeezed out,
oxidized on the air, rinsed, acidi?ed in usual
manner, rinsed again and soaped at the boil.
The cotton is dyed'fast reddish yellow shades.
are caused to react at about 150° C. with 15 parts
of Laminoanthraquinone in ortho-dichloroben
30
zene, as described in Example 5. The dyestuif
thus obtained is a yellow-brown powder dissolv
ing in concentrated sulfuric acid to a red solu~
tion and dyeing cotton from an orange-brown
vat yellowish orange shades.
When substituting 2-a1ninoanthraquinone for
What we claim is:
1. A vat dyestufl of the formula
wherein R1 stands for the radical of a compound
selected from the group consisting of 1:95:10
anthradithiazole and 1 : 9,5 : lil-anthradipyrazole,
the respective —CO-— groups being severally at
the l-aminoanthraquinone there is obtained a
tached to the two terminal benzene rings of the
yellow powder dissolving in sulfuric acid to a
radical R1, and each R2 stands for the same
yel1ow~red solution and dyeing cotton from an
radical of a vattable compound of the anthra
40
orange~brown vat strong yellow shades.
quinone series.
The di- (N) -methyl-1:9,5:lO-anthradipyrazole
2. A vat dyestu? of the formula
2:6-dicarboxylic acid chloride used in this ex
ample has been prepared as follows:
i—‘l
/\
11 parts of 1:5-dichloroanthraouinone-2:6
dicarboxylic acid, 66 parts of pyridine and 6.6 a‘ '
parts of methylhydrazine of 80 per cent. strength
are heated in an autoclave provided with a
Rz-NH-O o
c O—NH—"R2
\lQl
stirrer for 15 hours to 120-125” C. After cooling
the content of the autoclave is suction-?ltered
and washed with pyridine. The filter residue is 50 wherein each R2 stands for the same radical of
a vattable compound of the anthraquinone series.
boi‘ed up with dilute caustic soda solution and
3. A vat dyestuff of the formula
animal charcoal, the solution is ?ltered and the
di-(N) ~methyl - 119,5:10 - anthradipyrazole-2:6
dicarboxylic acid formed is precipitated with hy
drochloric acid. When ?ltered, washed and dried 55
it represents a yellow-orange powder dissolving
in sulfuric acid to a green-yellow solution and
melting above 320° C. with decomposition.
For the purpose of converting the compound
into the acid chloride '7 parts of the acid are 60
heated to boiling for 1/2 hour with a parts oi
CH3
thionyl chloride and 400 parts of dry ortho~di~
chlorobenzene, while stirring. After distilling
wherein each R2 stands for the same radical of
40 parts of the mixture the solution is suction’
a vattable compound of the anthraquinone series.
iiltered while hot and the ?ltrate is allowed to 65
It. A vat dystnff of the formula
cool.
The di-(N) -methyl - 1:9,5z10 - anthradi
pyrazole-2:G-dicarboxylic acid chloride is crys
tallized in yellow-orange needles which, after
wherein R1 stands for the radical. of a com
?ltering, washing and drying melt above 360° C.
70 pound selected from the group consisting of
with decomposition.
1 :9,5 : lil-anthradithiazole and 129,5:10-anthra
Example 7
dipyrazole, the respective -CO—- groups being
severally attached to the two terminal benzene
13 parts of di-(N) -methyl-1:9,5:lO-anthradi
rings of the radical R1, and each R2 stands for
pyrazole - 2:6 - dicarboxylic acid chloride are
75 the same anthraquinone radical.
caused to react with 23 parts of l-amino-‘l-ben
2,408,259 '
10
5. _The compound of the formula
8. A process for the manufacture of vat dye
stuff, which comprises reacting a dicarboxylic acid
halide selected from the group consisting of 35
1:9,5z10 - anthradithiazole
dicarboxylic
S——N
0100
acid 7
C 0 Cl
halides and '1 : 9,5 : IO-anthradipyrazole dicarbox
ylic acid halides containing the respective acid
halide groups severally ‘ attached to the two
terminal benzene rings, with two molecular pro
portions of an amino substitution product of ya vat
N—S
40
table compound of the anthraquinone series.
9. A process for the manufacture of a vat dye
stu?, which comprises reacting a dicarboxylic‘
acid halide selected from the group consisting of 45
1:9,5z10 - anthradithiazole
dicarboxylic
with two molecular proportions of Z-aminoan
thraquinone.
12. A process for the manufacture of a vat
dyestu?; which comprises reacting an anthra
dithiazole dicarboxylic acid halide of the formula
acid
halides and 1:9,5:10-anthradipyrazo1e dicarbox
ylic acid halides containing the respective acid
halide groupsseverally attached to the two ter
010C
0 0 G1
minal benzene rings, with two molecular propor- 50
tions of an aminoanthraquinone.
10. A process for the manufacture of a vat
dye-stuff, which com-prises reacting an anthra
dithiazole dicarboxylic acid halide of the formula
with two molecular proportions of 1-amino-5
_ benzcylaminoanthraquinone.
55
13.~ A process for the manufactureof a vat
dyestuif, which comprises reacting an anthra
dithiazole dicarboxylic acid halide of the formula
S——N
010 C
I
C O'Cl
‘00
010C
N—\S
Y
"
'
11. A process for the manufacture of a Vat
dyestuff, which comprises reacting anv anthra
dithiazole dicarboxylic acid halide of the formula
0001
Y
with two molecular proportions of an amino
anthraquinone.
ll
with two molecular proportions of l-amino-B
‘ chloro-anthraquinone.
'
THEODOR HOLBRO.
WALTER KERN.
_ PAUL SUTTER."
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