Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~7~
The present inventio~ provides a water soluble dyestuff having,
in the form of the free acid, the formula (1): -
~ N = N ~ ~ _ / 1 (1)
C 2 02S 2 C 2 OS03H
1 2 R4 R2
OS03H
in which Rl is hydrogen, alkyl having from 1 to 4 carbon atoms, benzyl, benzyl
substituted in the benzene nucleus by methyl and/or chlorine, or is hydroxy-
alkyl having from 2 to 4 carbon atoms ox hydroxyalkyl having from 2 to 4
carbon atoms and esterified with an inorganic or organic acid, cyanoalkyl
ha~ing from 2 to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido
or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the alkyl or
alkyelenemoiety, halogenalkyl having 2 or 3 c æ bon atcms, or halogen~alkenyl
having 2 or 3 caxbon atoms, R2 is hydrogen, methyl, ethyl or halogen, R3
is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro, R4 is hydrogen
halogen, methyl, ethylt me~hoxy, ethoxy, nitro, and a salt thereof.
More particulaxly, the present invention provides novel and valuable
water-soluble dyestuffs having t~ formula ~1) in the form of the free acid
~ N = N ~ N / Rl
--~ / \1=/ \ CH2-CH2-OS03H (1)
CH -O S ~ R4 R2
OS03H
-- 2 --
. ' ',
.
~7~
in which the radicals Rl to R4, identical or different to each other, have
the follcwing meaning: Rl represents hydrogen, aIkyl having from 1 to 4
carbon atoms, benzyl optionally substituted by methyl and/or chlorine, hydroxy-
alkyl having from 2 -to 4 carbon atoms, hydroxyalkyl having from 2 to 4 carbon
a-toms and esterified with an inorganic or organic acid, for example sulfato-
alkyl, phosphato-alkyl, acetoxyalkyl, propionyloxyalkyl or phenyl-sulfonyloxy-
alkyl, or represents cyanoalkyl having from 2 -to 4 carbon atoms in the alkyl
moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4
carbon atoms in the aIkyl or alkylene moiety, halogenoalkyl having-2 or 3
carbon atoms, preferably chloroalkyl, or halogenoalken~ having 2 or 3
carbon atoms, for example bromo- or chloroalkenyl, R2 represents hydrogen,
methyl or ethyl, preferably methyl, or a halogen atom, for example chlorine,
bromine or fluorine, preferably chlorine, R3 represents hydrogen, halogen,
for example chlorine, bromine
- 2a -
~a~
.
HOE 76/F 275
7~;~2
or fluorine, preferably chlorine or bromine, methyl or ethyl,
preferably methyl, methoxy or ethoxy, preferably methoxy or
~
nitro,
R4 represents hydrogen, halogen, for example chlorine, bro-
mine or fluorine, preferably chlorine or bromine, methyl
or ethyl, preferably methyl, methoxy or ethoxy, preferab-
ly methoxy, or nitro.
The dyestuffs of the instant invention of formula (1)
'`whërëin the~~-sulfato-ethy-lsul-on~l~group is standing in tha
diazocomponent in para-position to the azo group, are pre-
ferred, especially those dyestuffs which posse~s, in form
of the free acid, the general formula (1a)
.. . .. ... ~
~ N = N ~ ~1 j
CH2-0 S ~ R2 2 2 0s03H (1~. 3
03H
wherein R3 and R2 are defined as aboYe.
Especially preferred and advantageous in the dyestuff
having in form of the free acid the formula (lb1
, . _ . .. .. .. . . .. . . . ... ...
f~ N = N ~3 CE~2-CH
CH ~-O s~f CH2 -CX2-0s03H ~ lb)
CE2
OS03~
-- 3 --
HOE 76/~ 275
7~
The novel d~estuffs are preferably present in the form
- of their salts, especially alkali metal salts, for example
sodium or potassium salts, or alkaline earth metal salts,
for example calcium salts, and are used preferably in the
form of the aforesaid salts.
The present invention also provides a process for the
preparation of the dyestuffs of formula ~1) or of their
salts, which comprises diazotizing an aromatic amine of
the formula (2~
R3 --
~-C~2-CH2-o2s ~NR~
R4
. . . . . . ...
or a salt thereo~ prefexably an alkali metal or alkalin~
earth metal salt, in which R3 and R4 have the aforesaid mean-
ing and W stands for the hydroxy or sulfato group, and coupl-
ing it with a coupling component of the formula (3)
, . . .. , ., ., . ., .. .., ., .. ., .. _ . _ _ ... . .. .
lE~< '
~ 2 CH~-CM2-W
or a salt thereof, pre~erably an alkali met~l or alkaline
earth metal salt, in which ~1' R2 and W have the aforesaid
meaning, and, in the case o~ the preparation o~ a dyestuff
o~ the formula (4)
, .. , .. . , . . , . .. .. . , ; . ......
R3
~ N=N ~ R ~ ~~
! CH2-2S ~ \ ~4
IlH2 R4 l2 CH2-CH2-w
W
- . - : - -
', . ' ~ .
.
:. ,
HOE 76/F 275
7~
in which R1, R2, R3 and R4 have the aforesaid meaning and
one or ~oth radicals W represent hydroxy, transforming this
dyestuff of formula (4) into its ~ulfuric acid semi-ester
compound of formula (1) or its salts by means of a sulfa-
tization agent.
The acid compounds of formula (1) are transformed in-
to their salts or vice versa by methods known to the expert,
for example by neutralization or acidification with a strong
inorganic acid, for example sulfuric acid.
Suitable diazo components of formula (2) for preparing
the dyestuffs of the invention are especially
4-B-sulfatoethylsulfonyl-aniline,
3-~-sulfatoethylsulfonyl-aniline,
2-bromo~4-3-sulfatoethylsulfonyl-aniline,
2-chloro-4-~-sulfatoethylsulfonyl-aniline,
2-chloro-5-~-sulfatoethylsulfonyl-aniline,
2-bromo-5-~-sulfatoethylsulfonyl-aniline,
2,6-dichloro-4-B-sulfatoethylsulfonyl-aniline,
2,6-dibromo 4-~-sulfatoethy~sulfonyl-aniline,
2,5-dichloro-4-B-sulfatoethylsulfonyl-aniline,
2-methyl-~-B-sulfatoethylsulfonyl-aniline,
2 methoxy-5-B-sulfatoethylsulfonyl-aniline,
2-methoxy-4~B-sulfatoekhylsulfonyl-aniline,
2-methyl-6-chloro-4~B-sulfatoethylsulfonyl-aniline,
2,6-dimethyl-4-~sulfatoethylsulfonyl-aniline,
2,6-dimethyl-3-~-sulfatoethylsulfonyl-aniline,
2,5-dimethoxy-4-~-sulfatoethylsulfonyl-aniline,
2 methoxy 5-methyl-4 -B-sulfatoethylsulfonyl-aniline,
; 29 2-nitro-4-B-sulfatoethylsulfonyl-aniline,
-- 5 --
HOE 76/F ~75
a762~
4-nitro-2-~-sulfatoethylsulfonyl-a~iline,
or the B-hydroxyethylsulfonyl derivatives thereof.
- The compounds of formula (2) containing a B-sulfato-
ethylsulfonyl group can be prepared from the corresponding
B-hydroxyethylsulfonyl-anilines by esterification, for ex-
ample with water-containing or concentrated sulfuric acid
or with amidosulfonic acid, for example by adding the cor-
responding B-hydroxyethylsulfonyl anilines to an equimole-
cular amount of 60 % sulfuric acid and subsequently heating
in a manner analo~ous to the process descri~ed in German
Patent 1,150,163, or by dissol~ing the ~ hydroxyethylsul-
fonyl anilines in an excess of concentrated sulfuric acid
or 100 % sulfuric acid (monohy~rate) at room temperature
(i.e. at about 10 - 25 C~ or by reactiny with amidosulfo-
nic acid in the presence of pyridlne or a pyridine base ina manner analogous to the esterification process described
in German Patent 1,443,877. In the process of the invention
the ~-sulfatoethylsulfonyl anilines prepared in this manner
can be used directly in the form of the reaction mixture
; 20 obtained in the esterification, i.e. whithout isolation.
Suitable coupli~ components of formula ~3~ for pre-
paring the dyestuffs of the invention are especially the
following compounds.
N-B-sulfatoethyl-aniline, N-B-sulfatoethyl-N-ethyl-aniline,
N-~-sulfatoethyl-N-methyl-aniline, N-~-sulfat~ethyi-N-n-
butyl-aniline, N-~-sulfatoethyl-N-ethyl-3-methyl-aniline,
N-B-sulfatoethyl-~-ethyl-3-chloro-aniline, N-~-sulfatoethyl-
N-B-hydroxyethyl-3-~hloro-aniline, N,N-di-~-sulfa~oethyl-
29 aniline, N,N-di-B-sulfatoethyl-3-chloro-aniline, N-B-sulfato-
-- 6 --
.
.. ~ . .. .
,. :
. ,, . , . .. ~ - -
. . ~ . .
HOE 76/F 275
7~
ethyl~N-2-bromallyl-aniline, N~ sulfatoethyl~N-2-chloroal-
lyl-aniline, N-~-sulfa~oethyl-N-benæyl-aniline, ~-~-sulfato-
ethyl-N-B-carbonamidoethyl-aniline, N-B-sulfatoethyl-N-B-
carboxyethyl-aniline, N-B-sulfatoethyl-N-~-carbethoxyethyl-
aniline, N-e-sulfatoethyl-N-~-cyanethyl-aniline, N-~-sulfato-
ethyl-N-~-acetoxyethyl-aniline, N-~-sulfatoethyl-N-B-cyan-
ethyl--3-methyl-aniline, N-~-sulfatoethyl-N-~-hydroxyethyl-
aniline, or the ~-hydroxyethyl derivatives thereof.
The coupling components of formula (3) containing a
B-sulfatoethylamino group can be prepared, for example by
the methods described by K.H. S~unders, J.Chem.Soc. (London)
121, 2667 - 2675 (1922). Alternatively, they can be obtain-
ed by esterification of their B-hydroxyethyl-aniline deri-
vatives, for example by reacting same with sulfuric acid,
for instance 100 % sulfuric acid in the presence of chloro-
sulfonic acid or with sulfuric acid containing sulfur tri-
oxide (oleum)~ The coupling components oE formula (3) esteri-
fied in this manner can als~ be used in the process of the
invention directly in the form of the reaction mixture xe-
sulting from the esterification, i.e. in non-isolated form,
In the process of the invention the aromatic amines of
formula (2) can be diazotized by generally known methods.
; In further processing reaction components carring the group
of the formula ~SO2-CH2-CH2-OSO3H should not be subjected
to strong alkaline conditions. Compounds of this type as
well as compounds carrying the B-hydroxyethylsulfonyl group
are preferably coupled at a pH in the range o~ from l to 7
and at a temperature of rom ~5 to ~25 C.
29 The dyestuffs of formula (1~ prepared by the process of
-- 7 --
.- .- ... . . ~ .
.. . , : .
.
: '
~76~Z E 76/F 275
the invention can be isolated from the reaction solution by
salting out with an electrolyte, for example sodium chloride
or potassium chloride, advantageously after having adjusted
the reaction mixture to a pH of from 3.5 to 7Ø They are
then filtered off and dried. Alternatively, the dyestuffs
of formula (1) obtained according to the invention can be
isolated by concentration by evaporation or by spray-dry-
ing. When the reaction solution contains large amounts of
sulfate ions, it is recommended to precipitate same in th~
form of sparingly soluble salts prior to spray-drying, for
example by the addition of calcium carbonate. It is also
possible directly to use for dyeing the dyestuff solutions
obtained after the synthesis, optionally after adclition of
buffer substances.
When the coupling is carried out with diazo and/or coupl-
ing components of formula (2) ox ~3) in which W represents
hydroxy and the intermediate dyestuff of formula (4) is o~-
tained, this dyestuff (41, which i~ only sparingly soluble
in the aqueous medium in most cases, can be isolated direct-
ly by filtration, optionally after ha~ing adjusted a pH of
from 3.5 to 7Ø If precipitation of this dyestuff is not
complete, it can be completed by the addition of electro-
lyte. After drying, the isolated dy~stuffs o~ formula (4~
are trans~ormed into the sulfuric acid semi-ester dyestuffs
of formula (1). The esterification can be carried out in
a manner analogous to the process of K.H. Saunders mention-
ed above, for exam~le by reacting the compound~ of formula
(41 with h~ghly concentr~ted sulfuric acid in excess, for
example of 80 to 100 % strength, or with chlorosulfonic acid
-- 8 --
... . . , ... , ~ :
. : . . .: :
.: ., . ', : ' :
' ,' ': - - . , - , ~ . :
., , . ' .. . .
HOE 76/F 275
~7~;2~
in a non polar organic solvent. other esterification
- methods suitable for transforming the dyestuffs o~ formu-
la (4) into dyestuffs of formula (1) use amidosulfonic
acid as sulfatization agent in the presence of pyridine
or pyridine bases, or sulfur trioxide or chlorosulfonic
acid in an aprotic polar organic solvent, for example
N-methyl-pyrrolidone, dimethyl formamide or sulfolane
(tetramethylenesulfone).
The dyestuffs of formula (1) obtained after the esteri-
fication can be isolated as follows:
When the esterification has been carried out in an excess
of sulfuric acid, the esterification mixture is preferably
diluted with ice, the excess sulfuric acid is precipitated
by adding a calcium compound, for example calcium carbona-
te, the dyestuff solution is separated and the dyestuff isisolated from the filtrate obtained by salting out or spray-
drying, -
In the case of the esterification in a non-polar oxganic
solvent immiscible with watar with one of the aforesaid
esterification agents,for example chlorosulfonic acid,
water or ice are added, the mixtuxe is optionally neutraliz-
ed, th~ organic phase is separated and the dyestuff is iso-
; lated from the aqueous phase in the manner described above3-
With the esterification with amidosulfonic acid in pyridine
or a pyridine base, the esterification mixture is fixst
di~tilled in vacuo to recover the major proportion of the
__
pyridine or pyridine base. Further amounts of the pyridine
or pyridine base can then be separated in dilute form by
29 adding water and effecting another distillation. -
. g _
.
, ,, ,', ' ~ ~
, , ,
HOE 76/F 275
When the esterification is carried out in a polar, aprotic,organic solvent immiscible with water using sulfur trioxide
or chloroculfonic acid, the dyestuff can be precipitated by
adding methanol and filtered off with suction after neutrali-
zation with an alkaline agent, for example finely ground so-
dium carbonate, or the esterification mixture is diluted with
water, neutralized, the organic phase is extracted with methy-
lene chloride and the dyestuff is isolated from its aqueous
solution by spray-drying or salting out. -
The dyestuffs described in Example 1, 2 and 3 are espe-
cially preferred.
It is another object of the present invention to use
the dyestuffs of formula (1) for dyeiny and printing cellu-
lose fibers and natural or synthetic polyamide fiber materials.
Still another object of this invention is to provide a pro-
cess for dyeing and printing cellulose fiber material-and
natural or synthetic polyamide fiber materials by applying
a dyestuff of formula (1) on said fiber material and fixing
it thereon. Cellulose fiber materials are preferably cotton
and regenerated cellulose; for example ~iscose rayon, flax~
hemp and jute. Suitable polyamide fiber materials are espe-
cially wool and hairs of other animals as well as silk. Pre-
ferred synthetic polyamides are especially polyamide 6,6, po-
lyamide 6, polyamide 1~ and polyamide 4.
The no~el dyestuffs of formula (~ are especially sui-
table as reactive dyes~ they can be fixed fast on the afore-
said substrata by t-he method known for reactive dyes. On
cellulose fibers they yield by the exhaust process in a long
2g bath with the use of various alkali additives dyeings of a
- 10 -
". ' ' . ' ' .
~., .
,
,: '. , ~
~76~2
very good dyestuff yield Excellent color yields (tinc-
torial strengths) are also obtained by padding cellulose
fibers by known padding processes wherein the dyestuff is
fixed by means of an applied alkali while dwelling the so
treated material at room temperature or by subsequent steam-
ing or with dry heat. For printing, the usual One-Phase
process are suitable wherein a printing paste containing
an acid binding or alkali-yielding agent, for example so-
dium bicarbonate, sodium carbonate or sodium trichloroace-
tate, is applied on the material with subsequent fixationOf the dyestuff by steaming, for example at ~0~ to 103 C,
as well as the two~phase processes are suitable wherein a
neutral or weakly acid printing paste is printed on the
fiber material which is passed thereafter through a hot
~5 alkaline bath containing an electrolyte, or which is
cross-padded by an alkaline, electrol~te-containin~ pad-
ding liquor and the dyestuff is then fixed by steaming or
under the action of dry heat. ~ith these processes intense
prints with sharp out-lines and a clear white background
2Q are obtained. The quality of the prints is practically not
influenced by Yarying ~ixation conditions-and,therefore, the
constancy of the shades is satisfactory.
The dyeing and prints obtained with the dyestuffs OI
formula (1) on cellulose fiber materials are distinguished
by outstanding fastness properties. In this connection the
most important properties o~ manufacture and use should be
stressed, especially fastness to light, fastness to wet
processing such as fastness to washing at 60 and 95~ C,
29 fastness to acid and alkaline milling, fastness to water ~nd
, ~ . '' ~ ',
.
.
HOE ~
~7~iZ;~
sea water, fastness to acid cross-dyeing, fastness to alka-
line and acid perspiration and fastness to pleating, hot
pressing (ironing) and rubbing. Moreover, the dischargeabi-
lity to white af the dyeings is very good.
Natural as well as synthetic polyamide fiber materials
are preferably dyed with the novel dyestuffs of formula (1)
in an acid, aqueous dye bath or liquor. The desired pH ofthe
dye bath or liquor is preferably adjusted with acetic acid
or acetic acid and ammonium acetate or sodium acetate. To
obtain dyeings having a good levelness or to improve the
evelness of the dyeings it proved advantageous to add
the usual levelling agents, for example compounds on the
basis of a reaction product o~ a fatty amine, for example
stearyl amine, with an alkylene oxide, such as ethylene
oxide, and/or a reaction product of cyanuric chloride with
approximately the three-fold molar amount of an aminobenzene-
sulfonic acid and/or an aminonaphthalene-sulfonic acid. The
material is dyed in usual manner at a temperature of from
60 to 100 C, preferably by the exhaust process~ more espe~ -
2Q cially at the boiling temperature of the dye bath or in a
pressure dyeing machine at a temperature of from about 110
to 120 C.
The ~ollowing examples illustrate the invention~ the
parts being by weight unless otherwise stated, and the rela-
tion of parts by weight to parts by ~olume bein~ the same asthat o the kilogram to the liter.
E X A M P L E ~:
.~ . ...___. _ _
~2~4 Parts o~ 4-~-sulfatoethylsulfonyl--aniline were added
2~ while stirring to ~,200 parts by volume or water, ~43 parts
,
1~7~
of 31 ~ hydrochloric acid were added and the mixture cooled
to 0 - 5 C. At said temperature 80 parts by volume of an
aqueous 5N sodium nitrite solution were slowly dropped in.
Stirring was continued for 15 minutes, whereupon the excess
nitrous acid was destroyed with a small amount of amidosul-
fonic acid. Coupling to obtain the azo dye was performed
at a pH of about 1.8 to 2~0 by adding a solution of 98 parts
of N-B sulfatoethyl-N-ethyl-aniline in 400 parts by volume of
water, which solution had been neutralized by about 40 parts
of sodiu~ bicarbonate. When the coupling was complete the
pH was adjusted to 5.5 by adding about 65 parts of sodium bi-
carbonate, and the dyestuff was precipitated by adding potas-
sium chloride in an amount of 15 %, calculated on the ~l~me
of the solution, filtered off whith suction and dried at
60 C in vacuo. An orange-red dyestuff powder was obtained
with which clear reddish orange dyeings and prints could ~e
produced on cotton by the fixation methods as usual for reac-
tive dyes. In the form of the free acid the dyestuff had the
following formula
N -N - ~ / 2 CH3
~H2-O S 2 2 OSO3H
fH2
Os03H
E X A M P L E 2:
112.4 Parts of 4-~-sulfatoethylsulfonyl~aniline were di-
azotized as described in Example 1 and then coupled, instead
- 13 -
: .
:
.
HOE 76/F 275
~7$%~
of the coupling component used in Example 1, with a solu-
- tion of 150 parts of N,N-di-~-sulfatoethyl-3-chloroaniline
in 400 paxts by volume of water; the solution containing
the coupling component had a pH of 6.5 to 7.0 adjusted with
sodium bic~rbonate. After salting out with potassium chlo-
ride (in an amount of 25 %, calculated on the volume of the
dyestuff solution obtained), filtering with suction and dry-
ing, a brownish powder was obtained with which reddish-yel-
low dyeings and prints were produced on cotton by the known
fixation process for reactive dyes.
In the form of the free acid the dyestuff had the follow-
ing formula
....
S ~ ~=N ~ / C~l2 C~2 OSO3~
CH2-C~ -OSG3H
IH~-O2S Cl 2
CH2-0S03R
E X A M P I E 3:
59~3 Parts of N,N-di-~-hydroxyethyl-3-chloroaniline
were introduced at 25 to 28 C over a period of about 25 mi-
nutes into 49 parts of 100 % sulfuric acid. 43.8 Parts of
chlorosulfonic acid were then added dropwise ~at 70 to 75 C
over a period of several hours. Next, the esterification
mixture obtained was cautiously poured onto 200 parts of
ice and the pH of the solution obtained was adjusted to 1
by adding 63 parts of sodium bicarbonate.
- 70.3 Parts of 4-B-sulfatoethylsulfonyl-aniline were
- 14 -
~76Z~ HOE 76/F 275
suspended in 350 par-ts by volume of water and 150 parts of
ice and dissolvedfneutralized by adding about 15 parts of
sodium carbonatej 43.5 parts of a 40 % aqueous solution of
sodium nitrite were added to it at O to 5 C. For diazoti-
zation this solution obtained was slowly added which stirringto a mixture of 375 parts of ice and 70.5 parts of 31 % hy-
drochloric acid. After one houx, the excess of nitrous acid
was decomposed with a small amount of amidosulfonic acid~
the coupling solution described above was added and a pH of
1.9 to 2.0 was adjusted. After a stirring time of several
hours, the pH was adjusted to 5.5 to 6.0 by adding sodium
bicarbonate, the dyestuff precipitated by adding 440 parts
of potassium chloride, filtered off with suction and drie~.
A yellow-brown dyestuff powder was obtained with which red-
dish-yellow dyeings and prints were produced on cotton by
the known fixation process usual for reactive dyes.
The dyestuff represented a mixture of the following two
dyestuffs in a molar proportion of about 35:65.
- - .. ...... . ... ... . . . .
N=N - ~ CH2-CH2-OH (ca. 35 ~)
2-c~2-2s Cl CH2-CH2-OS03H
S03H
CH2-CH2-Os03H
N=N ~ (ca. 65 %)
~ CH -CH -050 H
CH2-CH2-02S Cl 2 2 3
OS03H
- ~5 -
HOE 76/F 275
7~i~2
E X A M P L E 4:
144 Parts of 4-B-sulfatoe~hylsulfonyl-2-bromoaniline
were dissolved in 400 parts by volume of water with the addi-
tion of 46 parts of sodium bicarbonate and 82 parts by volume
of an aqueous 5N sodium nitrite solution were added. The re-
action mixture was cooled to O to 5 C snd poured onto a mix-
ture of ~00 parts of ice and 143 parts by volume of 31 % hy-
drochloric acid, whereby the diazonium compound formed pre-
cipitated. Stirring of the mixture was continued for 15
minutes at O to 5 C, and the excess of nitrous acid was de-
composed with a small amount of amidosulfonic acid. For coup-
ling a solution of 98 parts of N-~-sulfatoethyl-N-ethyl aniline
and 40 parts of sodium bicarbonate in 400 parts by volume of
water was added to the diazonium solution obtained. Coupling
was continued at a pH of 1.8 to 2.0 while stirring for some
hours until completed. By adding 65 parts of sodium bicarbo-
nate a pH of 5.0 to 5.5 was adjusted; the dyestuf was salted
out by adding potassium chloride (in an amount of 15 %, cal-
culated on the volume of the dyestuff solution), filtered off
with suction and dried at 60 C in vacuo. The product was
ground. A red dyestuff powder was obtained with wich scarlet
dyeings and prints were obtained on a cotton fabric by the
known ixing methods usual for reactive dyes.
In the form of the free acid the dyestuff had the o~low-
ing constitution -
~ N N ~ ~ 2 3
F~2-o S CH2-C~2-
CH~
OS03~
- 16 -
-
HOE 76/F 276
E X A M P L E 5:
140 Parts of 4-~sulfatoethylsulfonyl-2,6-dichloroanili-
ne were diazotlzed by the indirect method as described in Ex-
ample 4. The subsequent coupling was effected with a solu-
tion of 86.8 parts of N~B-sulfatoethyl-aniline and 40 parts
of sodium bicarbonate in 400 parts by volume of water. The
azo dye obtained in this manner was isolated in analogous
manner as in the preceding examples. In the form of the free
acid it had the following formula
Cl
2l5 = ~ N~l_C~2-CH2-OSO3H
~H2
' CH2-OS03H
Yellowish-orange dyeings and prints were pxoduced therewi~h on
cotton fa~ric under the known fixing conditions usual for re-
active dyes.
E X A M P L E S 6:
2041 Parts of 4~B-hyroxyethylsulfonyl-aniline were intro
duced into a mixture of 3Q parts of concentrated hydrochloric
acid and 300 parts by volume of water, the mixture was cooled
to 0 to 5 C and diazoti~ed at said temperatur2 with 20 parts
by ~olume of aqueous 5N sodium nitrite solution. Stirring of
the mixture uas continued for 60 minutes and the exces~ of ni-
trous acid decomposed with amidosulfonic acid. For coupling a
solution of 13.7 parts of N-B-hydroxyethyl-aniline in 30 parts
- 17
: .
'
.: ,
HOE 76/F 27~
7~2
by volume of glacial acetic acid was added, while the pH of
the coupllng mixture was adjusted to and maintained at 1.8
to 2.0 by the addition of sodium bicarbonate. The coupling
mixture was stirred for some hours at 10 to 18 C, the preci-
pitated dyestu~f filtered of f with suction, washed with alittle 5 ~ sodium sulfate solution and dried at 60 C.
The dry product was introduced into 250 parts of 100 %
sulfuric acid and the mixture was stirred for 4 hours at 50
to 70 C. After cooling, the esterification mixture was cau-
tiously poured onto 1,400 parts of ice, the excess sulfuricacid was precipitated in the form of calcium sulfate by slow-
ly adding 235 parts of calcium carbonate in portions, the hot
reaction mixture was filtered off with suction and the preci-
pitate washed with hot water. The dyestuff solution obtained
as filtrate was spray-dried.
The dyestuff isolated in this manner yielded on cotton
orange dyeings and prints under the fixing conditions known
and usual for reactive dyes. In the form of the free acid
it had t~e formula
... , .. ~, .. . , . . , , .. , ~ .. . ... . .. ... ...
=N ~ H~CH2-CH2-O~O3H
fH2 2
.
E X A M P L E S 7 to 35:
The dyestuffs listed in the fol1Owing table were prepared
- according ~o the processes of the instant invention, especially
in a way a~ described, or analoyously thereto, in the aore-
said examples. They yielded likewise on cotton fast dyeings
- 18 -
~762~2
and prints in the shades indicated in the table.
Exam le formula of dyestuff shade on cotton
P
CH3
7 1 3S C~l2C~I2 02S ~ N==N- ~ N < orange
2 2 3
8 H35-CII2C~I2-2S- ~ N==N- ~ C2~15 orange
CH3 CH2 H2S 3H
Br H
3 2 2 2 ~ N==N- ~ N < orange
2 2 3
CH2CH2CH2CH3
0 N- ~ N-=N- ~ N bluish red
2 2 3
11 H03SO-CH2CH2-02S- ~ N==N- ~ N \ red
C112CH20S03H
Cl CH2CH2COOH
12 H03SO-CH2CH2-02S- ~ N==N- ~ N / orange
2 2 3
2 2 3
13 HO SO-CH2CH2-02S- ~ N^~ N < orange
CH3 2 2 3
CH2CH2CN
14 H3S-C~2CH2-2S- ~ N==N- ~ N / orange
- 19 -
~ , ... .
-
, : , . - ' :
,
~7~
Example formula of dyestuff shade on cotton
~CH2CH2CONH2
HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange
Cll2CH2OSO3H
CH2CH2 -CO-OC2H5
16 3 2 2 2 ~ N==N- ~ N \ orange
CH2C~120S3~1
CH2CH2-O-CO-CH3
17 3SO CH2CH2 2 ~N N ~N / orange
2 2 3
Br
CH2 -1=CH2
18 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange
CH2CH20S03H
Cl
~CH2 -C=CH2
19 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange
2 2 3
C 2 H2 3
HO3SO-CH2CH2-O2S- ~ N==N- ~ N / orange
OCH3 CH2CH3
21 ~ N =N ~ N orange
:~ Ho3so-cH2cH2-so2 2 2 3
22 HO3SO-cH2cu2-~2 ~ ~ \ C~l CH253H dd sh
_ 20 -
7~
Example formula o:E dyestuff shade on cotton
23 ~ ~ yellowish
3 2 2 2 \ CH2C~I20SO3H orange
24 ~ N==N- ~ -N \ orange
HO3SO-c~l2-cH2-so2 CH2CH2 S 3
H3CO CH2CH3
HO3SO-CH2cH2-02s- ~ N==N- ~ -N ~ reddish
OCH3 2 2 3 orange
26 ~ N-==N- ~ N orange
CEI CH OSO H
3 2 2 2 2 2 3
Cl / CH3
27 HO3SO CH2CH2 2 ~ ~ \ orange
CH3 2 2 3
28H3S-CH2CH2 2S- ~ N==N- ~ -N~/ orange
CH3 2 2 3
29 ~ ~ ~ orange
H3S-CH2-CH2 S2 CH3 H2 2 3
~ OCH3 / 2 2 2 3
30H3S-CH2CH2-2S~ ~ N==N- ~ -N \ orange
CH2CH20S3H
Br CH -CH
31~ -N==N~ ~ -N / orange
CH CH OSO H
- Ho3so-cH2-cH2-so2 2 2 3
-~ - 21 -
, ' :. ~ '
~976~:
F.xample formula of dyestuff shade on cotton
32 11~5-C~12CH2 2 ~ ~ < Cll CH 0503H orange
33 ~13S-cH2cH2-2s- ~ N==N- ~ N \ orange
Cl 2 2 3
34 H03SO CH2CH2 02S ~ N N ~ N \ orange
2 2 3
2 3
3 2 2 2 ~ N==N- ~ N / orange .
Cl CH2CH2S3H
- 22 -
' . , ' '
