Note: Descriptions are shown in the official language in which they were submitted.
1060436
German Offenlegungsschrift No. 1,955,849 describes the pre-
paration of reactive xanthene dyestuffs of the general formula
R ~ R'
~L so ~-)
\ N ~ / 3
(+) \ [W]m--A F (CH2)n ~ p ,,
wherein R and R' each represents hydrogen, halogen, hydroxy, alkyl, alkoxy,
carboxyl or a sulfonic acid group, Rl and R2 each represents hydrogen or
an alkyl group optionally substituted by halogen atoms or hydroxy, carboxyl,
sulfonic acid or phenyl groups or -OSO3H (sulfato)- or -HN-acyl groups,
which may form together with the nitrogen atom an alkylene-imine ring op-
tionally containing additionally hetero atoms, R3 is hydrogen or alkyl, A
represents a mononuclear or binuclear aromatic radical, such as phenylene :~
or nephthylene group or a diphenyl, diphenylamine, diphenyl sulfide, di-
phenylsulfone or azobenzene radical, which may be substituted at the aromatic
nucleus by halogen atoms, lower alkyl groups, lower alkoxy groups, carboxyl
or nitro groups, and W represents a bivalent bridge member such as the group
-CH2-, -CH2-CH2-, -NH-, -
-
~ CO-NH- ~ S02-NH-
~ '.
-- 2 --
` ~0 ~Q 436 HOE 73/~ 218
Y is a group of the formula
l4~
N ~ SO2- CH - C~12 or
/l41 ` .
t t~ so2 CH2 - CH2
.
wherein Z stand~ for the hydroxy group or for an organic or
inorganic radical capable of being ~plit off by alkalis,
R4 represents hydrogen or alkyl, m, n and q each represents
O or 1, and p;r~presents 1 or 2.
I The preparation is carried out by reacting one mol of
a dihalogeno-~anthylium compound of the general formula
\ /
, ' ' I~Lso (~) '' ' '
, - ~L ' ''.
- -
wherein the sub~tituents B represent chlorine or bromine atomsand R and Rl have the above meanings, with at least one mol of
an amino compound of the general formula
,,~, N - W ~ -A t ~C~2)n-~N )g~502~~Hz~Ch2_0~ p
: ~ ~herain R3, W, A, R4, m, n, p and q are defined as above,
F with an amine of the formula
-3-
~060436 HO~ 7~/F_218
~ 1
HN--
wherein ~1 and R2 are as defined above, in an aqueous, aqueous-
organic or organic medium between about 0 and about 120 C,
pre~erably between about 20C and about 80C, if desired in
the presence of an acid-binding agent, and by subsequently
reacting the mono-condenRation product thus-obtained with at
least one mol of an amine of the above formula HNR1R2 or of
the above-mentioned amino compound containing B-hydroxy-
ethylsulfonyl groups in an aqueous, aqueou~-organic or organic
medium between about 70 and about 200C, preferably betwe~n
about 90C and about 160C, in the presence of acid-binding :`
agents~ if desired the xanthylium compounds thus obtained of
the general formula
R\ 3.
S03 (-)
,,
N ~o~L ~R3 R
. E~]m A -(cH2)n_(l)q S02 ~}I2
." ', ' ~' ' ` : CH2
- OH P
. .
. ~ `
~herein R1, R2, R, R7, R3, R4, W, A, m~ n, q and p have the
` ~ aboYe-meanings, may be converted by treating them with
~ulfatizing agents, phosphorylattng agents, halogenating
agents, alkyl or arylsulfonic acid halides or carboxylic acid
~halides or carboxylic acid anhydrides into the xanthylium
.
:: -4-
... . : : ~ .
1060436 HOE 73/~ 218
dyestuffs of tho general formula, wherein Z represents the
group -O-S03H, -O-P03H2, halogen or -O-acyl, and if desired
the dyestuffs thus obtained may be converted b~treating them .
with alkaline agents, such as alkali hydroxide or alkali
carbonate, for example sodium hydroxide or sodium càrbona-te, .
into the corresponding dyestuffs wherein Y represents the
group R4
~(N)q S02-CH=CH2
and if desired the dyestuffs,thus obtained may be converted
. 10 by reaction (addition) with salt~ of the thiosulfuric acid,
with dialkyl amines or with phenol~ into the corresponding
dye~tuffs with Z of the radical -S-S03H tthiosulfato-)~ :
-N(alkyl)2 or -O ~ . -
However, it is necessary to effect an intermediate
1g l~olation of the intermediate products in this known procoss
which are formed during the condensatiQn reaction, before
they are used in the eubsequent processes.
It ha~ now been found that this disadvantago of an inter- ¦
mediate isolation of the products can be avoided and that the
process it~elf may be generally improved technically and
economically when the process is carried out in a purely
- or anic medium using specified solvents.
Thus, the present invention relates to a novel and .
impro~ed process for preparing reactive xanthene dyestuff 8
of the general formula (1)
`~:
- -, . , . : -
. : .
1060436
R ~ R'
~ SO3 (~
\ N ~ N / R3
R2 (+) ~ CH2] m --A ~ ~CH2)n ] p
.: -
wherein R and R' represent hydrogen atoms, halogen, such as fluorine, chlor- .
ine or bromine atoms, or hydroxy, alkyl, alkoxy, carboxy or sulfonic acid :
groups Rl and R2 each represents hydrogen or an alkyl group unsubstituted,
or substituted by halogen atoms or hydroxy, carboxy, sulfonic acid or phenyl
groups or -OSO3H ~sulfato-) or acylamino groups or both may form together
with the nitrogen atom an alkylene-imine ring optionally containing addi-
tionally hetero atoms, for example of a piperidine or morpholine ring, R3
represents hydrogen or alkyl, A is a mononuclear or binuclear aromatic ra-
dical, for example a phenylene or naphthylene radical or a diphenyl ether,
diphenyl-amine, diphenyl-sulfide, diphenyl-sulfone or azobenzene radical,
which may be substituted on the aromatic nuclei by halogen atoms, lower alkyl
groups, lower alkoxy groups, hydroxy, carboxy, sulfo or nitro groups, and Y
is a group of the formula
R4
N ~ SO2-CH=CH2 ~2)
or
4~
N ~ SO2-CH2-CH2-z (3)
q
wherein Z stands for sulfato, phosphato, halogen or O-Acyl wherein "Acyl"
is the acyl radical of an alkyl or aryl carboxylic acid or for the hydroxy
group, R4 represents hydrogen or alkyl, m each is O, 1 or 2, n represents
O or 1, and p is 1 or ~.
The improvement of this novel process, which is carried out by
- 6 -
1060436
reacting one mol of a dihalogen-xanthylium compound of the general formula
(4)
53 (4)
B /~\ B
wherein the substituents B are chlorine or bromine, R and R' have t~e above
meanings with at least one mol of an amino compound of the general formula :~ .
(5) :~
N- ~ ~ m A ~ (CH2)n ~ N ~ 502-CH2-CH2- ~ (5)
wherein R3, A, R4, m, n, p and q have the above meaning, or with an amine ~s
j: of the formula (6~
Rl
1 ~ ~ 10 1~ (6)
r~ ~ R2
wherc m Rl and R2 have the above meanings, in a purely organic medium be-
tween about 0 and about 140C, preferably between about 20C and about
~ : llOCi optionally in thc prcsence of an acid binding agent, and
J~ by subsequently reacting the monocondensation product thus obtained, after
neutralizing the acid formed, with at least one mole of an amine of the
,~
.3~ mentioned~ formula (5) or of the formula (6), respectively, between about
70D and about 200C, preferably between about 90 and about 160C, in the
~ presen~cc of acid-binding agents, esterifying, if desired, the xanthylium
,~ compounds:obtained of the general formula (7)
~ :
D 7 _
;~ ' :
~ . . . . . .. .
1060436
R ~ R'
~ SO3(-)
\N ~ N ~R3
R2 ~ [CH~ID At(CH2)ntN~502-CH
wherein Rl, R2, R, R', R3, R4, A, m, n, q and p have the abo~e meanings, by
means of sulfatizing, phosphorylating or halogenating agents, alkyl- or
aryl-carboxylic acid halides or carboxylic acid anhydrides, to form the
xanthene dyestuffs of the mentioned formula (1), wherein Z is the group
-OSO3H, -OPO3H2, halogen or -O-Acyl as defined,
and if desired, converting the dyestuffs thus obtained by treating them with
alkyline agents, for example alkali hydroxide or alkali carbonate, such as
: sodium hydroxide or sodium carbonate, into dysstufs of the general formula
(1~, wherein Y is the group
/R \
~ -N; - SO2-CH=CH2
,~ :
is characterized by carrying out the reactions mentioned without isolating
an intermediate stage in a solvent containing a carbonamide group which is
optionally N-alkylated, especially in a solvent selected from the group con-
sisting of an acid amide or N-alkylated acid amide of an open-chained ali-
phatic or cyclic aliphatic carboxylic acid, or in a solvent which is a N-
alkylated acid a~ide of an inorganic acid, or in another polar aprotic sol-
vent.
Alkyl and alkoxy groups for the radicals R, R', Rl, R2, R3 and
~: 20 R4 are~especially those which contain 1 to 5 carbon atoms in the alkyl ra-
dical. Halogen atoms and acylamino groups according to the radicals Rl and
R2 are especially chlorine and bromine atoms or lower alkane- or alkene-
carbonylamino groups or aromatic acylamino groups, for example phenyl-
~ .~
: ~ - 8 - ;~;
:
106~)~36
sulfonylamino or benzoylamino or phenylsulfonylamino or benzoylamino
groups substituted in the nucleus by chlorine, methyl, ethyl, nitro, cyano,
slllfo, carboxy, methoxy, ethoxy, carbonamide or sulfonamide groups. The
0-Acyl radical for Z is preferably a lower alkylcarbonyloxy radical, or an
aromatic carbonyloxy radical, for example benzoyloxy or a benzoyloxy radical
substituted by chlorine, methyl or sulfo.
Among the compounds prepared according to this new process those
are preferred, for which the substituents and radicals of the above-men- -
tioned general formula (1) are defined as follows:
R and R', identical or different, each represents hydrogen, fluorine, chlor-
ine, bromine, a hydroxy, carboxy or sulfonic acid group, a lower alkyl or
lower alkoxy group, especially a methoxy and ethoxy group;
Rl and R2, identical or different, each represents hydrogen or an alkyl
group having 1 to 3 carbon atoms, which may be substituted by a phenyl ra-
dical or a hydroxy, carboxy, sulfonic acid or sulfato group, or a cyclo-
hexyl radical, or
Rl and R2 together with the nitrogen atom represent a piperidine or mor-
pholine ring;
R3 stands for hydrogen or a lower alkyl group, especially a methyl or ethyl
group;
R4 stands for hydrogen or alkyl having one to 4 carbon atoms;
A represents the phenylene or nephthylene radical or the diphenyl, diphenyl-
ether, diphenylamino, diphenyl sulfide, diphenylsulfone or azobenzene ra-
dical, whereby A may be substituted in the aromatic nuclei by halogen,
hydroxy, lower alkyl, lower alkoxy, carboxy, sulfonic acid or nitro groups;
.
Z means hydroxy, an -0-Acyl radical of a lower alkyl or alkylphenyl car-
boxylic acid, such as the acetoxy radical, phosphato, sulfato or a halogen
atom, such as chlorine or bromine. The term "lower" refers to an alkyl
radical having 1 to 4 carbon atoms.
In the improved process of the invention, among the organic sol-
D g
. . . ... .. ~ . . ~ .
106()436
vents used as reaction medium in the course of the condensation processes,
namely, in the first condensation step of the dihalogeno xanthylium com- -
pound of the formula (4) with an amine of the formula (5) or (6) and in
the subsequent condensation step of the monohalogeno-xanthylium compound
obtained from the first condensation step, with an amine of
- 10 -
- ~060 43~ H~ ~ 8
the formllla (6) or (5), respecti~ely, and used as reaction
medium in the subsequent con~ersion of the xanthylium compounds
obtained of the formula (7) into those of the formuIa (1),
the following ones have proved to be especially advantageou~:
acid amides, ~uch as f'ormamide, N-methyl and N-ethylformamide,
N-methyl and N-ethylacetamide, and polar aprotic solvent such
a~ N,N-dimethyl- and N,N-diethylformamide, N-N-dimethyl-and
N,N-diethylacetamide, N-methylpyrrolidone, tetrame.~hyl-urea,
hexamethyl-phosphoric acid triamide and sulfolane; N-methyl-
tO pyrrolidone may be particularly mentioned.
Starting compounds for the reactions according to the
process of the in~ention are especially the following ones:
For the dihalogen compounds of the.formula (4) there may be
mentioned:
3~6-dichloroxanthylium-9-phenyl-2~-sulfonate, 3~6-dichloro-
xanthylium-9-phenyl-4~-sulfo-2~-~ulfonate, 3,6-dichloro-
xanthylium-9-phenyl-4'-methoxy-2'-sulfonate, 3,6-dichloro-
xanthylium-9-phenyl-4~-ethoxy-2~-sulfonate,3,6-dichloro-
xanthylium-9-phenyl-4~-carboxy-2~-sulfonate, 3,6-dichloro-
xanthylium-9-phenyl-4'-hydroxy-5~-carboxy-2~-sulfonate, 3,6-
dibromo-xanthylium-9-phenyl-4~-chloro-2~-sulfonate and 3,6-
dichloro-xanthylium-9-phenyl-4'-chloro-2~-sulfonate.
. Amine~ of the formula (5) cuitable according to the
process are for examples 4-aminophenyl-B-hydroxy-ethylsulfone,
4-aminobenzyl-B-hydroxy-ethylsulfone, 4-aminophenethyl-B-
hydroxy-ethyl 8ul fone~ 4-(~ -aminomethyl)-phenyl-B-hydroxy-
-. ethylsulfone, 4-(~ -aminoethyl)-phenyl-B-hydroxy-ethylsulfone,
3-hydroxy-4-amino-phenyl-B-hydroxy-ethylsulfone, 3,6-dimethyoxy-
29 4-amino-phenyl-B-hydroxy-ethylsulfone, 3-methoxy-4-amino-6-
.
. . .
- ~ . .
.: : ~ .: . ,
.
1060 436 H0~ 7~/~ 218
methyl-phenyl-~-hydroxy-ethylsulfone, 3-aminophenyl-B-hydroxy-
ethylsulfone, 3 aminobenzyl-~-hydroxy-ethylsulfone, 3-amino-
6-methoxy-phenyl-B-hydroxy-ethylsulfone, 3-amin~-4-methoxy-
phenyl~-hydroxy-ethylsulfone, 3-amino-4-hydroxy-phenyl~
hydroY.y-ethyl3ulfone, 3-amino-4-carboxy-phenyl-B-hydroxy-ethyl-
~ul~one, 3-amino-4-methoxy-benzyl-~-hydroxy-ethylsulfone,
2-methyl-5-amino-benzyl-B-hydroxy-ethylsulfone, 5-amino-2-
methyl-m~xylylyl- ~1, ~ 3-bis-sulfonylethanol, 4-aminobi-
phe~lylyl-4~ -hydroxy-ethylsulfone), 5-a~ino-naphthyl-1-
10 methylene-~-hydroxy-ethylsulfone, 5-amino-naphthyl-1-~-hydroxy-
ethyl~ulfone, 6-aminonaphthyl-1-(B-hydroxy-ethyl-sulfone),
4-amino-2~-nitro-diphenylamino-4~ -hydroxy-ethylsulfone),
2-methyl-4-amino-azobenzene-4~ hydroxyethylsulfone), 2,4-
dimethyl-3-aminophenyl-B-hydroxy-ethylsulfone, 3,5-dimethyl-
15 4-amlnophenyl-B-hydroxyethylsulfone, 2-methyl-5-t-butyl-3-
aminophenyl-B-h~droxyethylsulfone, 3-chloro- and 3-bromo-4-
aminophenyl-~-hydroxyethylsulfone, 4-chloro- and 4-bromo-3-
aminophenyl-~-hydroxyet~ylsulfone, 3-sulfo-4-aminophenyl- and
4_~ulfo-3-aminophenyl-B-hydroxyethylsulfone.
Aminee of the formula HNR1R2 suitable according to the
process are especially n-propylamine, diethyl amine, cyclo-
hexyl amine, piperidine, morpholine, benzyl amine, phenethyl
amine, B-amino-ethanol, aminoacetic acid, iminodiacetic acid,
taurine or N-methyl-taurine.
Acid-binding agent~ used in the condensation reaction,
are preferably inorganic compounds such a~ sodium hydroxide,
~odium hydroxide, sodium bicarbonate or sodium carbonate as
well a~ the corresponding potassium compound~, expediently
29 in a pulverized form.
-12-
.,, ... : - :
,
, ,, . , . . - .. : . : ' ,,, , - - -
1060436 HOE 73~F 218
Suitable sulfatizing agents are for example concentrated
sulfuric acid, olewn in different concentrations, sulfur
trioxide, chlorosulfonic acid, amidosulfonic acid or other
compounds yielding sulfur trioxide. Suitable phosphylating
age~lt~ are for example concentrated phosphoric acid, pyro~,
meta- or polyphosphoric acid, polyphosphoric acid alkyl esters
or mi~tures of phosphoric acid and phosphorus(V)-oxide. A~
halogenating agents there may be used for example thionyl
`chloride or thionyl bromide. As acylating agents there may
be used for example acetanhydride of acetyl chloride.
The xanthene dyestuffs of the general formula (1) obtained
according to the process of the invention are isolated by
precipitating them with another solvent, optionally after
neutralizing the reaotion mixture with alkaline agents, as
for example ~odium hydroxide, sodium carbonate, sodium bi-
carbonate, sodium acetate or the corresponding potassium
compound~. i
As precipitating agents may be used for example carbon
tetrachloride, chloroform, methylene chloride, acetone,
methanol, ethanol, butanol and benzene.
In contradistinction to the process described in &erman
Offenlegungsschrift No. 1,955,849, the new process has the
following advantagess
Since in the novel process the condensation and the
subsequent esterification of secondary reactions in the
radical Y are carried out without intermediate i~olation,
the improvement of the process of the invention i8 especially
advantageous in view of the fact that the precipitation and
29 dryin~ prooedure of the xanthylium compound~ of the formula (7)
-13_
1060436 HOE 7 31~' 2 1 8
are no longer necessary. This implies a considerable saving
of time. Eurthermore, the use o~ an organic solvent for the
purely organic reaction medium means that the amounts of
e~terification agents necessary for converting the dyestuffs
of the formula (7) into those of the formula (1), such as
sulfatizing, phosphorylating, halogenating and acylating
agent~, are considerably reduced. Thus, in the werking up, ¦~
the large amounts of sulfates, phosphates, chlorides, bromides
~nd acetates do no longer occur. The novel process has the
further advantage that considerably smaller reaction volumes
can be used and that the space/t~me yield is considerably :
increased,
Furthermore the solvents used in the process as reaction
medium or precipitating agent - the filtrates are mostly
S solv~nt~ - can ~e regenerated by distillation with a good
yield and u~ed again for the purpose indicated. In contra- ;~
distinction to the process described in German Offenlegungs-
~chrift No. 1,955,849~ by which the compounds of the formula
(7) are isolated by salting out and therefore, waste-waters
having a strong salt concentration are obtained, problems
concerning wa~te-waters and the above-mentioned mineral salt-
~as well as ecological provisions caused by them, need no longer
be considered in the novel process.
Furthermore, the novel process provides improved yields
with regard to the known process.
The following Examples illustrate the invention. Parts
and percentages are by weight unless ~tated otherwise. The
relationship of parts by weight and parts by volume is as grams
29 to cubic centimeters.
~14~
', , ' : : '~ ' '
. .
. ' . ' ' '
106~436 HOE ~3~` 21$
E X A M P L E 1:
20.1 Parts of 3-aminophenyl-B-hydroxy-ethyl-sulfone were
reacted at 90C with 3,6-dichloro-xanthylium-9-phenyl-2~- 1
sulfonate in 150 parts of N-methylpyrrolidone or dimethyl- i
formamide. After the end of the condensation, the hydro-
chloric,acid formed was neutralized with sodium carbonate
and the whole was further reacted at 110C for 3 hours with 1`
16.1 parts of N-methyltaurine-sodium and ~.3 parts of sodium
carbonate. Within 2 hours and at a temperature of 40-50 C,
,10 20-33 parts of chlorosulfonic acid were added and the
dyestuff formed was isolated b~ diluting with methanol and
neutralization with a methanolic sodium or potassium hydroxide
'solution. The dyestuff precipita ed as sodium or potassium
~alt was filtered off, washed with methanol and dried. It
corresponds in tho form of the free aoid to the formula
f"~ S03(~
H035-C~z-cH2~ ~ 502-Cli2-C112-0503
It was obtained as a red brown powder which dis~olved in
water with a bluish red color and yielded on cotton in the
p~resence of sodium bicarbonate very ~rilliant bluish red
dyeings and prints having a good fastness to washing.
The same dyestuff wa~ obtained if in the e~terification
in~tead of chlorosulfonic acid the equivalent amounts of
sulfur trioxide or a 65 ~ oleum were used.
., - - . ~
. .
-
1060436 HOE 73/~ 218
E X A M P L E 2:
The operation was carried out as described in Example 1
ancl instead of chlorosulfonic acid 35 parts of~amidosulfonic
acid were used. After esterification a~ 105 C t~e whole was
cooled and the dyestuff which was obtained as ammonium salt
wa~ precipitated with methylene chloride. After washing with
methylene chloride and drying, a dark red powdcr was obtained,
which dissolved in water with a bluish red color and yielded
on wool bluish red dyeings fast to washing.
E X A M P L E 3- -
20.1 Parts of 4-aminophenyl-B-hydroxy-ethyl-sulfone were
reacted at 100 C with 3.6-dichloro-xanthylium-9-phenyl-2'-
sulfonate in 200 part~ of N,N-dimethyl-acetamide. When the
condensation was finished the resulting hydrochloric acid was
neutralized with sodium carbonate~ the whole was further
conden~ed at 115C for three hours wlth 16.1 parts of N-methyl-
taurine-sodium and 5.3 parts of sodium carbonate. Then it
was esterified with 30 part~ of chlorosulfonic acid in two
hours at about 50 C and subsequently neutralized with sodium
carbonate, while cooling. When the neutral point was reached,
6 parts of sodium carbonate were added and the whole was heated
for half an hour to 55 C. The sodium carbonate still present
was neutralized with glacial acetic acid, the mixture wa-
~precipitated with acetone, filtered, washed with acetone and
dried. The dyestuff which corresponds in the form of the free
acid to the formula
. ,
-16_
. : . . - - - , . . . - . . , . :
... . - . .. . : .
., , . . : . , ~
. : : ~ : , . . . . . . .... . .
. ' . ~ ' , . . ~ . . , , , ~ . '
.. ~. . . ' ~ . ~ ' ' . ', '.... . ' .
" ",',',',',' ' ~' ' '. '' ' ''' ' '" '1''', ,.""' " '' ' '~ ' ' ' '
~060436 HOE 73/~ 218
~1 50 (-)
}10 ~ ~ J~ S02~ =C~I2
H3 (~) ~
,
was obtained as a red violet powder, dissolved in water with
a bluish red color and yielded on cotton fabrics very brilliant
printing samples havlng a good fastness to washing.
E X A M P L E 4:
- 40.5 Parts of 3,6-dichloro-xanthylium-9-phenyl~2~-sulfonate
were dissolved at 80-85C in 200 parts of N-methyl-acetamide.
At this temperature, 16.1 parts of N-methyltaurine-sodium
were slowly introduced. After ~tirring for some time the
mixture wa~ neutralized with 5.3 parts of ~odium carbonate ~o
that the reactlon mixture always remained slightly acidic,
and ~ub~equently 20.1 parts of 3-aminophenyl-B-hydroxy-ethyl-
sulfone were introduced and additionally 5.5 parts of sodium
carbonate. After stirring for some time at 140C the con-
densation was finished~ and the whole wa~ esterifisd with
24 parts of sulfur trioxide at 50C. The mi~ture was diluted
while cooling, with ethanol. Then it was neutralized, while
cooling, wtth 105 parts of potassium acetate, the precipitated
potassium salt of the dyestuff, which corresponds in the form
of the free acid to the formula of Example 1, wa~ filtered off
and wa~hed with ethanol. After drying a red violet powder
was obtained which dissolved in water with a bluish red color.
-17-
. . .
; .
! ' , ., ., ~ , , ,,, . ~,
6~)436 ~ 218
E X A M P L E _~:
26.5 Parts of 4~ aminomethyl)-phenyl-B-hydroxy-ethyl-
sulfone in the form of the salt of the hydrochloric acid were
mixed with 40.5 parts of 3,6-dichloro-xanthylium-9-phenyl-
2l-sulfonate in 185 parts of hexamethyl-phosphoric acid
triamide. 5.5 Parts of sodium carbonate were a~ded. At 85C,
5.5 parts of ~odium carbonate were still added in the course
Or about 24 hours, so that the reaction mixture alway~
remained slightly acidic. ,-
16.1 Parts of N-methyltaurine-sodium were introduced and
5.4 parts of sodium carbonate were added; the mixture was
stirred at 110C until the end of the reaction. Then it was
esterified with 29 parts of chlorosulfonic acid for two hours
at 40-50c and worked up as described in E~ample 1. The dye-
1g ~tuff which corresponds in the ~orm of the free acid to the
f ormula
~ ' ~ S03(-) ' , , ''
N0 S-CH -CH
3 2 2~
C~3 ~ ( ) , ~ ~ 502-CH2-C~2_oso3H
was obtained as a red powder, dissolved in water with a bluish
red color and a yellow fluorescence and yielding on cotton in
the presence of alkaline agents very brilliant dyeings and
prints.
E X A M P L E 6~
The condensation was carried out as described in E~ample,l
-18_
- , ,
.,: : . - ; .; . : . .
1060436 HOE 73~F 218
or 4 and instead of chlorosulfonic acid or sulfur trioxide
45 parts of acetic acid anhydride were added, and stirring
was continued at 105 C until the reaction was finished. The
dye~tuff formed which corresponds in the form of the free acid
to the formula
~~SO (~) '
3 CH2-CH2 ~ NH ~
, ~ (,,) , . , So2cH2cH2-ococH3
was precipitated with-acetone, filtered off and washed with
acetone. A red violet powder was obtained which dissolved in
water with a bluish red color and yielded on cotton, when
treated with alkali~, very brilliant bluish red dyein~ and
pr1nts,
E X A M P L E 7s
. If the reaction was carried out as in Example 6, but if
instead of acetanhydride 36 parts of thionyl chloride were used
for the reaction at 45C, a dyestuff was obtained as a red
violet powder which corre~pond~ in the form of the free acid
to the formula
~o3s-cN2-c~z ~ N~l ~ SO CH OH Cl
~ C~13~ (~) z z 2
-19-
, ' ,'.: : .. . : .
.,,, , ,
., ,~ . : ~,, : ,
1060436 HOE 73/F 218
It had similar properties as the dyestuff described in
Example 6, `
The dyestuffs listed in the following Table can be .
prepared in sim.ilar way. They yield on cellulose fiber
materials dyeings and prints having similar good fastness
properties.
.
,.
' .
.
.
-20_
~ ~ .
1060436 - ,
HOE 7 3 /Ii` 2 1 8
Q) Q)
o h h h h h
,S .q .c ,1~
o u) o~ Q
~ ~ .,1 ~ .,1 .,1 ~ .
.q o ~
., ~ .,
P~ o~
o U~ o o o
o U~
o , o o o
, . C~t , , . ,
~ m ~ ~ ~
:r: vc~ .
p~Y m
v~ '~ v~ v~ 1'
o O C~ O O
.,, . ~ ~\1 X ~ 0~ ~
'', ~ '. . - ~. .
~$ +
/ \ ~ ~
~;
m~
o 0~ ~o~ '
:~ :C I
~ o o
:~
V C~ V V~
. . . ~ m ~ .
. . ~. C~V, , V ~ . C> . .
. ,, . . .
. . .,. .
x m ~ m
.
P~ .
'
_ .. . ... . . ..... ,., .... _ ., _ _ .. ~.... 1
: . -21- .
.
: . . . . . . .. .
~. , ., .. ., , , :, . . - . , : , ..... ..
; : : : , '' ': ' - : -
~: . . ." . : - : . : , .
1060436 HO~ /E` 218
~ 0 0 0
o h h h ~ h ,~
~ o
tt ~ P :~ P ~ o ~ o ~ o
~ O ~ 1 0
U~ (.) ,t~ ,c ~ h :~
... .. ~ W~ p ~
O ' O C) O
. ~ U~
V ~ ~ N
. ' ' , ~, .,- .
. . , . . ''
, i , ' ' ~
o ~ o o o u~ o
. "N ~ pN ~N ~N ~ N
. V V V ' V O O V -
. ,.
'; $ ' ~ , , tr S~ p~ , ~ , p~
' ~; I .',
O ~ N
, . . . ' .
., ' . ~ ~ O . ,
. ..... . , . . _ .. .... .. _ , .. . . . ., . . ... _ . . . .. ..
--22-- ~
.. ~ . ` .: - . , , :
. - ` ' , : . ~ . ` , :
1o6o436 HOE 73/F 218
,
o h h h h
,,~1 0 Q ~ .Q h n h . ;.
p~
~ O O
- o' o
. ' ' U~ C~l ~ j
'W~
, o o o ~ U~ V C~
o . o- o ,~ q o o
. m ~N ~ P oc~
m" :~ ~ Q o~ o~ 1 o ~3
C~l C`l O ' Ctl U) ~ V) ~y N ~ l
o o -- o ~ m ~ m
~, b~
K
. , . .
., . , , .
~ ! ~ ~ ~ ' t~ ~ ' t~
. . . . ' . , , . ' . . ~1~
~h ' C~ o, , O O
~ C`l t~ ~ ~1 ~ N
V ~ X
.IPC ' . ~ I I I I I I
' ~'
~ m
.,
.. 1 . . . .. .
~ ~ u~
--. . ~ . .
23
.. .. . . . . ..... . . . . ... ...
. ~
~. ., . ~. - ~ . . .: -
~ ` ~060436 HOE 73/F 21 8
~ O
u~ o ~ h~ h P h h :~ ~ h ~ ~ ~ h
. 0~ 0~ I 0~ 0~ ' .
. O o o O ~ O O
~t`l ~N N O ~ ~1`1 5N
. N CY .t`l $ ~ ~ N C~
O O ' O ' O C~P: O O
U~ U) O t~lV U~
., ,. ~,'~'...................................
~, ~ ,
. . r . . . ~
. , ~ , , . ..
P~ ~, ' $ :~: $ $ ' $~ P: . .
' . .
. $ $ . S~
, . $~ ' $~ ' $ ; ' P~ .
O O O O O O O
,,u) o~ '
~C~I ~N ~ `1 p~ xN
C~l N N ~1 t`t ~`1 N
, ~ "
. I
~ ~ $, IS 1 $, $,
. ~ , ~ ., . , ,;
, , . .
O ~- .- N t'~
. N C~l N N
--Z4-- .
, ~:: ~: . . ,
lQ60436 HOE 73/~ 218
'o
O Q~ 0
~ ~~ o ~ o ~ ~ ~ o
,q o ~ 1 0
1/~ 0 h ~ .Q h h ~ ~ h ~ h ,~ h ,Q ,,,
m~ .
. o :' ,
o~ m~
U) t) ~
~ m'`' ~ x~
. N U O O
m.
C~ o o o o o o o
C~ U) ~
I ~ C~l ~ C~l ~ ~
C~ ~ O U C~ C) U C~ -
O , ~ ~ ~ ~ t~l N N .
u) , ~, m P~
~ O :: o o o O o o . .
I , x U~
)~
,
,, .
.
.~ ~ m ~ m~ .
~; . I , , , 1, 1 ,,
., . ^, ~ .
' O~ ~
. ~ N
. ' C~ U U C.) C~ U Ir~ U~
. N ~ N ~ N
v ~ r P N
~: .
K
~: ~ . , .. , . - - o
. . - . '
'' .. . . . . . --
--2~--
, . .
,:,, ., - ' . -,, : : .. , ., . . . .` -
1060436 HOE 73/F 218
o h h h h h h
o
o
O
' `- P~
p~ l .o
~ ~ ~~ . U~ ~ C~' i
o o .0 o C~ o o
. O ' O , O O N . o o
I I I . I ~ , , . .
c~ t MM U M M
V V C) ~ V C) , .
V ' ~ O V O V
.. O O o o :~ I o o
x ~
~ l
. iN ~
I ~
. \/ ' ' : ' '
O ,'
- 11 ' l~jl ' o~ o~ o~
' ~`~ U~ . U) 'J~
T Ic~ ~' N
. ' ~ ' ' ~ V V ~ V
~ ~ ~NC~
P~ ~ V~ C~ V
I ~ .
- . '
, '.
_, . ~ X 15 W , W, W
.' . ...
.. ..
,
P; Pl $ t~ P . P~ PZ t~
~ ~ , - ~ CO O~ O ~
..
. .
-26_
.- ~ . , , . -- .. - . ~ :
- . ~
~: - . ~ . - ~: , , ` - ,, `
, . . . , -. ; . :
~060436 H0~ 7,?l~ 218
.
O h h h h
o
O o o
~ O
O' O ~ V C~ ~ Vo o
I I N N , I N V U~
:c p ~ m ~ ~ O O
V V C~l I C) N N
~ I p N I ~ p~
cy ,~ r~ , OC~t V p~ ~3 V
O V O .U~ ~ I N V V
~ U~ N
P~ V O V O
¦ O _ O ~ ~_U I IIJ ~N ~3
. , . ~ .
)~ ~ :
. ~ $
' '. V V . ~ , ,0 V V .X~
,,.
. ' '
" UO)
,V ' ' O' t) V V O ~
. . I~N ~N 1~ ~ C,) V V
. il I ,'1 ''1' 1. 1 1.
. ' , ,'" '
. . ' .
. .
.. . ~ ' ~ ' ' ' ; -
, ~,, .
.. ,, , , , , . , ~ . , .
: . . - - ... .
- . ` . . ., -. . . - ,., :
. . : ' . . . : - ' . : . ~
.: - . :. . :
