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Патент USA US3076697

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United States Patent O??ce
a
3,076,687
‘Patented Feb. 5, 1963
1
2
3,076,687
‘10 g. of sulphothiomorpholide are stirred at 90-100° C.
for 1 hour with 50 cc. of dimethyl sulphate, the solution
‘PROCESS FOR THE PRODUCTION OF WATER-7
SOLUBLE DYESTUFFS AND DYEING CELLU
LOSE THEREWITH
is diluted with 250 cc. of acetone, the resultant sulphonium
~ methyl sulphate of the tetramethylated copper phthalo
.
.cyanine teterasulphothiomorpholide is separated, thor
Helinut' Klappert, Koln-Stammheim, and Otto Bayer,
Leverkusen-‘Bayerwerk, Germany, assignors to Far-ben
fabriken Bayer Aktiengeseilschaft, Leverkusen, Ger
oughly washed with acetone and air-dried.
Yield: 13 g. of a blue powder which readily dissolves
in water with a greenish blue colour.
many, a corporation of Germany
No Drawing. Filed Mar. 20, 1959, Ser. No. 800,662
Claims priority, application Germany Apr. 16, 1958
9 Claims. (Cl. 8—54.2)
' Example 2
10
‘It has been found that water-soluble dyestuffs are ob
tainable by converting dyestuif pigments containing thio
morpholine or its C-substitution products linked via a
sulphonamide grouping, into the water-soluble sulphonium
groups with dialkyl sulphates'or trialkyloxonium boron
?uoride.
As dyestuff pigments a great variety of pigment dye
stu?‘s are suitable such as the tetra-aza-porphines, phthalo
From 17 g. of 4,4',4",4"'-copper-phthalocyaninetetra
sulphonic acid (prepared by an urea melt of 4-sulpho
phthalic acid) treated at 80° C. with 120 g. of chloro
sulphonic acid and ,22 cc. ‘of thionyl chloride, the tetra
chloride is obtained. ‘The moist sulphochloride is washed
neutral and pasted with 100 cc. of ice water; the mixture
is cooled to 0° C. and 10 g. of thiomorpholine and 4 g. of
sodium bicarbonate are added. It is subsequently stirred
at 0° C. for 4—5 hours and then at room temperature
cyanines, azo dyestuffs, anthraquinone dyestuffs or oxazine
dyestuffs. The sulphonamide linkage does not necessarily
link directly the dyestuif molecule to the thiomorpholine,
but other groups may be interposed. The production of
the dyestuff pigments linked via a sulphonamide-like link
overnight. After ?ltering by suction, washing with water
phochloride groups with thiomorpholine.
dyeings on cotton have a somewhat more reddish shade
and drying, 17 g. of tetrasulphothiomorpholide are ob
tained. The product thus obtained is stirred at 90-100”
C. for 2. hours in 80 cc. of diethyl sulphate, the sulpho
nium salt is precipitated with 400 cc. of acetone and air
age to the thiomorpholine may be carried out, for ex 25. dried. Yield: 23 g. of pale blue crystalls which readily
ample, by reacting. dyestu?s containing one or more sul~ j dissolve in cold water with a bright blue colour. The
than that obtained with the dyestutf described in Example
1. In place of the diethyl sulphate, an equivalent quantity
halide, the process can be carried out using an excess of 30 of triethyl oxonium boron ?uoride [(C2H5)3O]BF,)
The dyestuffs may be reacted with thiomorpholine in
an aqueous suspension. To bind the liberated hydrogen
thiomorpholine as well as in the presence of other acid
.may be used.
binding agents such as pyridine or sodium bicarbonate.
The reaction is advantageously performed at tempera
Dyeing may be carried out in the following manner:
3 parts by weight of the dyestuif are dissolved in 2000
parts by weight of Water containing 2 parts by weight of
tures‘ of 0° C. to approximately 25° C. It is-advantage
ous to treat the thiomorpholine reaction products with 35 sodium acetate. 100 g. of a cotton yarn are treated in this
dyebath for 40 minutes at a rising temperature and for
the dialkyl sulphates or the trialkyl oxonium boron ?uo
ride-said alkyl groups being preferably lower alkyl
groups-which are used at least in an equimolecular ratio,
preferably in excess, at elevated temperatures, for ex
a further 15 minutes at 90—100° C. The yarn is then
rinsed and after-treated in an“ aqueous bath containing
5 cc./l. of sodium hydroxide 38° Bé. at 100° C. for 15
ample at 80—110° C. in the presence or absence of sol 40 minutes, To remove the super?cially‘ adhering pigments,
vents. The Water-soluble sulphonium salt thus formed
may be isolated from the reaction mixture, for example
by precipitation with acetone. Suitable ‘solvents are inter
tl'lie yarn is vigorously soaped; it is then dyed a turquoise
s ade.
Dyeing may also be effected in the following manner:
A cotton fabric is impregnated at 25° C. on the foulard
45 with an aqueous solution of 20 parts by weight of the dye
or xylene.
.
Some of the sulphonium salts thus obtained are soluble ' stuff in 1000 parts by weight of water, squeezed and dried
in cold water and some in hot water. They draw onto ' at 60-70" C. The fabric is subsequently after-treated
at l00° C. in a winch vat for 15 minutes with a liquor
materials consisting mainly of cellulose or regenerated
containing 15 cc. of sodium hydroxide 38° Bé. per litre of
cellulose such as cotton from a neutral bath and are split
water, and then soaped in conventional manner. The
to given again the insoluble sulphonthiomorpholides by a
fabric is then dyed a turquoise blue.
’ usual alkaline after-treatment‘ preferably at temperature
Printing with the dyestuff may be carried out as follows:
about 100° C. By this method dyeings are obtained hav-‘
‘alia dioxan, glycol dimethyl ether, chlorobenzene, toluene
ing very good fastness properties such as fastness to light,
to boiling with soda, to wet treatment and perspiration
A paste consisting of
' 40 g. of the dyestu?
55
and resistance to creasing and ironing.
The following examples are given for the purpose of
illustrating the invention without limiting it thereto.
40 g. of lactic acid
25 g. of trisodium phosphate
500 g. of tragacanth thickening
'
Example 1
12 g. of copper phthalocyanine are sulphochlorinated
50 g. of sodium acetate
345 g. of water
is printed on cotton or staple ?bre. After the usual pre
in 120 g. of chlorosulphonic‘acid at 135-140° C. The
solution is poured onto ice and ?ltered off with suction,
drying at 60° C., the dyestuif is ?xed on the ?bre by
neutral steaming in ‘the Mather-Flatt for 10 minutes.
and. the residue is washed neiitrah The moist tetrasulpho
After treating the fabric in conventional manner, beauti
' chloride is pasted ‘with 100 cc. of. ice water, cooled to 0° C. 65 ful bright blue prints are obtained of excellent fastness
' and 10 g. of thiomorpholine and 15 g. ‘of pyridine are
properties such as fastness to light, boiling with soda and
' then added. The mixture is then stirred for 4-5 hours and to wet processing as well as resistance to creasing.
‘ at 0° C. and subsequently at room temperature overnight.
It is then ?ltered off with suction, washed with water and
“ dried. Yield 21 g. of copper phthalocyanine tetrasulpho 70
diurn carbonate'solution.
t
t
-
I
Exztmple'fl
When in the process described'inwExample 2 instead
of 4,4',4",4”'-copper phthalocyanine-Jtetrasulplionic acid
.thiomorpholide which is insoluble in a boiling dilute so
I
,
-
there is used 4,4',4'.',4’.’-'-nickel phthalocyanine-tetrasul
3,076,687
4
3
obtained by coupling diazotised Z-arnino-anisole-4-sulpho
thiomorpholide with 2-hydroxy-naphthoic acid(3)-2-tolu
phonic acid, a dyestut‘r‘ is obtained which dissolves with a
green colour ‘and dyes cotton in turquoise green shades
having similar fastness properties as those of the dyestulf
obtained according to Example 2, especially a good fast
idide are stirred at 90-100" C. for 1 hour with 60 cc. of
dimethyl sulphate. The sulphonium salt is then pre
cipitated with acetone and isolated.
12 g. of ‘a dark red dyestuff are obtained which is
Example 4
scarcely soluble in cold water, but dissolved in hot water
The trisulphochloride from 4,4',4"-copper phthalo
with a bright red colour and dyes cotton in bright red
cyanine-tnisulphonic acid (prepared by an urea melt of 3
shades.
mols of 4-sulphophthalic acid and 1 mol of p-hthalic
Instead of the above dyestulf the following azo dye
acid) is obtained according ‘to the processdescribed in 10 stuffs
may be used which dye cotton in the shades in
Example 2. The moist sulphochloride is pasted with
dicated
below
100-200 cc. of water. 10 g. of thiomorpholine and 4 g.
ness to chlorine.
of sodium bicarbonate are then added at 0° C. and the
' mixture is stirred for 4-5 hours at 0° C. and then for
some hours at room temperature. After ?ltering with 15
‘
cal-on,
orn-oo-on-oo-nrn-Q
suction, washing and drying, 19 g. of trisulphothiomor
pholide are obtained. The product obtained is stirred at
90-100“ C. for 1 hour in 100 cc. of dimethyl sulphate,
and diluted with 400-500 cc. of acetone; the sulphonium
salt is ?ltered off with suction, thoroughly washed with 20
acetone and air-dried.
Yield: 27 g. of a pale blue powder which dissolves in
cold water with some more di?icul'ty than the dyestuft‘
obtained according to Example 2.
25
Example 5
The sulphochloride of 20 g. of 4,4"-copper phthalo
cyanine-disulphonic acid (prepared by an urea melt of
2 mols of 4-sulphophthalic 'acid and 2 mols of phthalic
acid) is reacted with thiomorpholine as described in
Example 1. 16 g. of dry disulphothiomorpholide are thus
obtained.
The product is stirred at 90-100“ C. for l-2 hours
with 70 cc. of dimethyl sulphate, the sulphonium salt is 35
then precipitated with acetone, ?ltered o? with suction,
washed with acetone and dried. 20 g. of a blue dyestu?
are thus obtained which is scarcely soluble in cold water,
but readily dissolves in hot water with a blue colour, and
which dyes cotton in bright blue shades.
Example 6
11 g. of dibenzo-tetramethyl-tetra-azaporphine copper
(prepared from 2 mols of Z-amino-S-imino-isoindolenine
and 2 mols of Z-amino-S-imino-3,4-dimethylpyrrolenine) 45
are reacted with chlorosulphonic acid as described in Ex
ample l to give the disulphochloride. The moist sulpho
chloride is washed neutral and pasted with 100 cc. of ice
Water. 10 g. of thiomorpholine and 4 g. of sodium bicar
bonate are then added at 0° C. The mixture is subse
quently stirred at 0° C. for 4-5 hours, and then at room
temperature for several hours. After ?ltering with suc
tion, washing and drying of the solid portions 15 g. of
Example 8
disulphothiomorpholide are obtained. They are treated
at 90-100” C. for 1 hour with 80 cc. of dimethyl sulphate,
and the dyestu?‘ is then precipitated with acetone and iso
10 g. of disulphothiomorpholide of the following for
mula
OIL-Cg:S
lated. Yield: 17 g. of greyish blue crystals which dis
SOs-N
solve in water with a dark blue colour, dyeing cotton
in grey-blue shades.
Instead of dibenzo-tetramethyl-tetra-azaporphine cop— 60
per there may also be used dibenzo-dimethyl-diethyl-tetra
|
O
l
NH-
\
_0H3
/
CH2—CH:
|
aza-porphine copper or nickel or dibenzo-ditetra-hydro
CHz-CIIz
benzo-tetraeza-porphine copper. Dyestuffs giving similar
shades are thus obtained.
65
Example 7
10 g. of the azo dyestu? of the following formula
prepared from the disulphochloride of 1,4-di-p-toluido
OCH:
N=N—
OH
-soi-
in
anthraquinone and thiomorpholine are heated to 90
100° C. for 1-2 hours with 80 cc. of dimethyl sulphate.
The sulphonium salt is precipitated with acetone. 12 g.
of a greyish black dyestuff powder are obtained which
dissolves in water with a grey-blue colour and dyes cot
CH3—CE2s
\
CHa-C?r
ton in grey-green shades.
75
Instead of the above dyestutf, the following dyestuffs
soc/ems?
may be used which dye c‘ cotton in the shades indicated
(prepared by converting tetrasulphonic acid into the tetra
beiow:
sulphochloride and reacting it with thiomorpholine) vare
0
CHz—CHa
/
S
\
NH
_-0H,
ll
t
' .
\
N--SO2
/
CHr-CH:
CHr-CI-h
.
/
Oa-N
S violet
vCline-43 I
CH3~
-—NH (I)
'CHrOIh
S
‘
N—}SO:
\CHrC?:
I
CH3
I blue '
CH3 '
sOPN'
‘
s ’
CH2—C§Q
' heated to 90-100" C. for 1-2 hours with 80 cc. of dimethyl
30‘ sulphate. The sulphonium salt is then precipitated with
acetone yielding dark blue crystals, and isolated.
‘
bi‘! ht blue
7‘
13 g. of a dark blue dyestu? are obtained which dis
. 0
‘ H
_
g
‘
- solve ‘in warm water'wi-th a deep blue colour and dye
CH2; Cm
I
0
cotton in reddish blue shades.
\
NH-
SOr-N
35
‘
v
3 v '
tun-on,
I
'
'
I
'
_ _
.
‘
'
NH
Instead of the above dyestulf, the following dyestu?is
vmay be used which dye cotton in the shades indicated
below:
_
'.
0
a
/ \.
‘
u
‘
'
_
f
CHg-C I:
\o
’
'
\S
\
‘
\N
CHr-OHi
CH2"'CH2
——SO2—-N/
“
\
S\
,
.
N
/ 1
CHr-CHQ
/
I
'
i
I
>
\ /
"
-
'
OH CF
NH
v
v
i
.
r
"2
O2—-N
'
'
blue
S
_
t
/
CHPCHQ
.
/CHz—CH_m
‘ 's\
7
C1
‘
CH9
/N~O2S_
/
7
0
i
/'
so N/
‘
_ _\N/
1
Example
9
y
.
'
‘ " CHPC€§~
>'QH2’—‘CHB
s
’
‘
I
“
N-ms-
‘
‘
'
In,‘
N
t
O
\(lHroéa
'
/
GHQ-CH1
o
I
‘
'
10 ‘g. of the tetrasulphothiomorpholide of an oxazine
dyestuff of the following formula
f/CHz-CHA
S\ ’
N~O2S
on CH
CHECK’
>
’
t .
N/
01
CHr-Céz
'
z—
\Cég
:
P \2s
1t
vio e
_ \oHrcéz
'
_
v
‘ 3,076,687
————SO2
N/
8 blue
/
CH2~CH¢
to obtain a thiomorpholide in which the thiomorpholine
We claim:
1. A phthalocyanine dyestu?”: containing a sulfothio 10 moiety is linked to said aza-porphine pigment in the form
of a sulionamide, and reacting said thiomorpholide with
morpholide group.
diethyl sulfate at a temperature within the range of
2. A process for the preparation of a water-soluble
about 90° C. to 100° C. to obtain the water-soluble sul
dyestutf from a water-insoluble pigment comprising react
fonium salt.
ing a compound selected from the group consisting of a
7. A process for the preparation of a water-soluble
7 metal phthalocyanine, a tetra-aza-porphine, anthraqui 15
dyestuff from a water-insoluble 1,4-di-para-toluido-anthra
none, and an oxazine dyestuff, with chlorosulfonic acid to
quinone pigment by reacting said water-insoluble ‘pigment
obtain the corresponding sulfochloride, converting said
sulfochloride to a thiomorpholid'e, in which the thiomor
pholin'e moiety is linked to said pigment in the form of a
sulfonamide, and reacting the resulting sulfothiomorphow
with chlorosulfonic acid at a temperature within the
range of about 135° C. to 140° C. to obtain the tetra
20 sulfochloridc, and thereafter reacting with thiomorpho
lide with a compound selected from the group consisting
of lower dialkyl sulfate and lower t-rialkyl oxonium boron
?uoride, to obtain the corresponding water-soluble sul
fonium dye salt.
line to obtaina thiomorpholide in which the thiomor
pholine moietyv is‘linked to said toluido anthraquinone
pigment in theform of a sulfonamide, and reacting said
thiornorpholide with diethyl sulfate at a temperature with
3. A process for the preparation of a water-soluble 25 in the range of about 90° C. to 100° C. to obtain the
water-soluble sulfonium salt.
dyestutf from a water-insoluble copper phthalocyanine
8. A process‘ for the preparation of a water-soluble
pigment by reacting said water-insoluble pigment with
ozazine
dyestuff from a water-insoluble oxazine pigment
chlorosulfonic acid at a temperature within the range of
by reacting said pigment with chlorosulfonic acid at a
about 135° C. to 140° C. to obtain the tetrasulfochloride,
and thereafter reacting with thiomorpholine to obtain a 30 temperature within the range of about‘ 135° C. to 140° C.
to obtain the tetrasulfochloride, and thereafter reacting
thiornorpholide in which the thiomorpholine moiety is
with thiomorpholine to obtain a thiomorpholide in which
linked to said copper phthalocyanine pigment in the form
the thiomorpholine moiety is linked to said oxazine pig~
of a sulfonamide, and reacting ‘said thiomorpholide with
ment in the form of a sulfonamide, and reacting said
dimethyl sulfate at a temperature within the range of
about 90° C. to 100° C. to obtain the water-soluble tetra 35 thiomorpholide with diethyl sulfate at a temperature with
methylated copper phthalocyanine tetrasulfothiomor
pholide.
Y
4. A process for the preparation of a water-soluble
in the range of about 90° C. to 100° C. to obtain the
water-soluble sulfonium salt.
9. A process for the dyeing of textile material con
taining at least one member selected from the group con
dyestuff from a water-insoluble 4,4',4",4”’ copper phthal'
ocyanine tetrasulfonic acid pigment by reacting said water 40 sisting of cellulose and regenerated cellulose which com
prises converting a water-insoluble pigment as employed
insoluble pigment with chlorosu-lfonic acid at a tempera
in claim 2, having a thiomor-pholine moiety linked to said
ture within the range of about 135°C. to 140° C. to ob
pigment in the form of a sulfonamide, and treating said
tain the tetrasulfochloride, and thereafter reacting with
pigment with a member selected from the group consist
thiomorpholine to obtain a thiomorpholide, in which the
ing of di-lower alkyl sulfate and tri-lower alkyl oxonium
45
thiornorpholine moiety is linked to said copper phthalo
cyanine pigment in the form of a sulfonamide, and react
ing said thiomorpholide with ([(C2H5)3O]BF4) to obtain
the corresponding water-soluble salt.
5. A process for the preparation of a water’soluble dye
stuff from a water-insoluble nickel phthalocyanine tetra
sulfonic acid pigment by reacting said water-insoluble
pigment with chlorosulfonic acid at a temperature within
the range of about 135° C. to 140° C. to obtain the tetra
sulfochloride, and thereafter reacting thiomorpholine to
obtain the thiomorpholide in which the thiomorpholine 55
moiety is linked to said copper ph-thalocyanine pigment
in the form of a sulfonamide, and reacting said thiomor
pholide with diethyl sulfate at a temperature within the
boron ?uoride to obtain the water-soluble sulfonium salt
and then treating said textile material with said water-so
luble sulfonium salt and subjecting said textile material
to an alkaline after-treatment.
Referencesv Cited in the ?le of this patent
UNITED STATES PATENTS
2,419,334
2,744,105
2,841,577
2,883,373
2,933,896
Conn et al. __________ __ Apr. 22,
Barney ______________ __ May 1,
Strobel et al. ________ __ July 1,
Bossard et a1. ________ __ Apr. 21,
Strobel et a1 ___________ __ May 31,
1947
1956
1958
1959
1960
range of about 90° C. to 100° C. to obtain the water-solu
OTHER REFERENCES
dyestuif from water-insoluble dibenzo-tetramethyl-tetra
Venkataraman': “The Chemistry of Synthetic Dyes,"
vol. 1, Academic Press Inc., publ., New York, 1952, pp.
aza-porphine copper pigment by reacting said pigment
475 and 697.
sulfochloride, and thereafter reacting with thiomorpholine
and 1139.
60
'ble su-lfonium salt.
6. A process for the prepartion of a water-soluble
>
.
Venkatararnan: “The Chemistry of Synthetic Dyes,”
with chloro-sulfonic acid at a temperature within the
range of about 135° C. to 140° C. to obtain the tetra~ 85 vol. 2, Academic Press Inc., publ., N.Y., 1956, pp. 1138
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