Note: Descriptions are shown in the official language in which they were submitted.
107~693
Prom German O~enlegungsschri~t No. 2 017 764 water-soluble benzo-
xanthene and benzothioxanthene dyestuffs of the general ~ormula (I)
i` I 1 i ~O
R'
. _
are known, in which X is an oxygen atom or a sulfur atom, Y is an oxygen atom
or a , N-R-group, wherein R is hydrogen or an optionall~ substituted alkyl,
cycloalkyl or aryl radical, a heterocyclic radical, a hydroxy or amino group,
and R'l and R'2 represent h~drogen atoms, halogen atoms, alkyl or alkoxy groups
and n stands for an integer of 1 to 3. The compounds of this formula ~I) are
prepared by sul~onating in known manner compounds of the general formula (II)
O
~ 1 ~ (Il)
. R'2
~herein R'l, R'2, X and Y have the above meanings.
The Of~enlegungsschrift does not contain any data about the position
of the sulfo group in the benzoxanthene-/benzothioxanthe~e body since in the
. ~ ,. ....:~.
.
. .
- :, . : . ,, ~
. . . - . ,
~ 1070693
course of sulfonation m~xtures of isomers are apparently~ formed; in this pro-
cess sulfonation takes place exclusively in the aromatic rings, preferably on
the benzoxanthene or benzothioxanthene dyestuff nucleus. Accordingly, no
compounds are described which carry a sulfonic acid group in the side chain
, N-R-group in final position. For in this known process, fuming sulfuric
acid is preferably used to effect the sulfonation of the nucleus; with the
rather low temperature of 70 - 100C a mixture of mono- and disulfonated pro-
ducts ~Example 1) is formed, at higher temperatures of 125 - 130C, however,
a product is obtained the nuclei of which are sulfonated twice (Example 2).
German Offenlegungsschrift No. 2 150 879 als~ d~scribes the use of such
; nucleus-sulfonated dyestuffs of the formula ~I) for the dyeing and printing
of fibr0 materials of natural and synthetic polyamides and polyurethanes.
Moreover, it describes dyestuffs carrying in the aliphatic side chain a sul-
fonic acid group via the imide, N-R; but they additionally contain at least
. i , .
;~ a further sulfonic acid group in the benzoxanthene or benzothioxanthene ring
~ skeleton.
These dyestuffs sulfonated in the benzoxanthene and benzothioxanthene
nuclei provide very brilliant dyeings, but with regard to some properties they
do not entirely comply with the requirements for dyestuff in our day. Espe-
cially the sensitivity towards alkalis of the dyeings prepared with these dye-
~ stuffs is cr~ticized. Furthermore, they do not provide even dyeings on materi-
als of texturized polyamide fibres showing different drawing.
~,
Now, better novel water-soluble compounds have been found which do
not contain sulfo groups in the benzoxanthene and -thioxanthene skeleton and
~" correspond in the form of the free acid to the general formula (1)
- 2 -
~ ., ":
., . "
,,,.. ,,. , - - , :
:
-
" ' ' ' ' ' ' ': , .
.
~070693
R ~ D)n
. X ~1)
R2 R4
Especially the alkali metal and alkaline earth metal salts thereof
as well as ammonium salts are preferred. As alkali salts there may be men-
tioned the sodium and potassium salts.
In the general formula (1) X is oxygen or sulfur, Rl, R2, R3 and
R4 are identical or different and each of them is hydrogen, halogen, espe-
cially chlorine or bromine, hydroxy, nitro, alkyl having 1 to 4 carbon atoms,
preferably the methyl or ethyl group, or alkoxy having 1 to 4 carbon atoms,
preferably the methoxy or ethoxy group, B is an alkylene radical having 1 to
6 carbon atoms, such as -CH2-, -CH2-CH2- or -CH2-CH2-1CH-CH2-, a cycloaliphatic
~ group, as for example a cyclohex~lene radical, or CH3
r a radical of the formula
-NH-, -NH-S02-, -NH ~ , -NH ~ -O-CH2-, -0-CH2-CH2
or a three-valent nitrogen atom a benzene or naphthalene or a benzyl radical,
the aromatic nuclei of which may be substituted by alkyl and or alkoxy radi-
cals each having 1 to 4 carbon atoms and or chlorine and may contain alkylene
` radicals having 1 to 4 carbon atoms, to which the radical W is bound, D is a
benzene radical, naphthalene, carboxylic acid ester, carboxylic acid amide or
ac~l radical of a lower aliphatic carboxylic acid, of the benzoic acid or
2Q naphthoic acid or an aliphatic or aromatic sulfonic acid amide radical,
pre$erafily~ a phenylsulfonic acid amide or p-toluene-sulfonic acid amide
- ' .
'
'. ~ ' , ., ' ' , ' '', "~ ' ~ -
.
",
, : , :
,................................... . :
. 070693
radical, a sulfamoyl or carbamoyl radical or a radical of the ormula
-O-CO-R, -NH-CO-R, -N(alkyl)-CO-R,
-NH-S02-R, -N(alkyl)-S02-R, -S02-NH-R,
-CO-MH-R or -CO-N(alky~l)-R, -S02N~alkyl)-R,
wherein R is a straight-chain or branched alkyl radical having 1 to 6 carbon
atoms or the phenyl radical, which may be substituted by chlorine, methyl,
ethyl, methoxy and/or ethoxy groups (the various alkyls mentioned above stand
~or alkyl or alkylene radicals having 1 to 4 carbon atoms, preferably 1 to 2
carbon atoms, such as for methyl or ethyl or methylene or ethylene), W is a
sulfo, sulfato, thiosulfato, phosphato, phosphonic acid or phosphonic acid
semi-ester group ~-PO(OR5)(0H) or its alkali salt), wherein R5 is an alkyl
radical having 1 to 5 carbon atoms or a benzyl radical bound to B and/or D
or 2, n is O or 1.
The novel compounds of the formula ~1) may be prepared in different
ways, for example
a) by reacting, in one reaction step, the dicarboxylic acid or the
anhydride thereof of the general formula ~2) or ~3)
.,
Rl ~ COOH RR3 0
~COOH
' ~ X J~ ~X ~
R2 R4 R2 ~R4
. (2) (3)
.~ith an amine o~ the general ~ormula ~4)
,~
. -- 4 --
,.'~, ~
. ~
.,,~ . , .
'. ~,
: : :
,
1070693
H2N ~ B ~D) ~ ~W)m
wherein Rl, R2, R3, R4, B, D, W, m and n have the above meanings, to form the
imide, or
b) b~ introducing the water-solubilizing group W into suitable imide
derivatives of the above-mentioned benzoxanthene or benzothioxanthene-dicarb-
ox~lic acids of the formula (2) which contain in the imide radical the above-
mentioned radical B or D or B-D~
Yariants o~t~e method b) are, for example the following ones:
1. Reaction of the hydroxy compound of the formula ~5)
R3 O
Rl ~ N ~ B-(D)n ~ m
1~ R ~ X
:' 2 4
wherein Rl, R2, R3, R4, B, D, X, m and n have the above meaning, but with the
proviso that the hydroxy group is not directly bound to an aromatic radical,
~ith a corresponding esterifying agent, the group W thus introduced being one
.of the above-mentioned ester radicals, except the thiosulfate radical;
2. lntroduction of the water-solubilizing group W which is already
contained in bound form in a molecule portion of the radical B or D or B-D,
~, for example b~ reaction of compounds of the formula ~6)
., .
.
~ ~ - 5 -
';
. :i........ , . . . . ,~, :
.: . -~
. . .
. - , . , ~ .: ~: - .
', ' : :' ~ ' '
-, ' , . ' ' - : , . . :
.
- lQ7~693
~3
Rl ~ N - E - Z
~ ~ O (6)
wherein Rl, R2, R3, R4 and X have the above meanings, E is a molecule portion
of the radical B or D or B-D with a terminal -CH2-group and Z is a hydroxy
or amino group, with a corresponding compound of the formula (7) completing
the radical of the formula members B, D or B-D,
. A G ~ )m ~7)
: wherein A is the radical of the formula Cl-S02- or Cl-CO, G is the remaining
: completing part of the radical B, D or B-D, as for example the radical R
defined in formula (1), or by reaction of compounds of the formula (8)
R3 0
R 1 ~N - E - Z
1() 2 ~J~o (W)!n ~8)
~th-~a c~rre~pondin~ compound of the formula (9) completing the rest of the
~ormula memBers B, D or B-D
A - G ~ (~)m (9)
'
_ 6 --
.
:.............. "' ' ~
.
1070693
~erein Rl, R2, R3, R4, E, Z, A, G and ~ have the above meanings, ml is the
integer 1 or 2 and m2 stands for zéro or 1 and the sum (ml ~ m2) is 1 or 2.
The above-mentioned reaction of condensation of compounds of the
formula (2) or ~3) with compounds of the formula (4) is preferably carried
out in a solvent at temperatures between 50 and 200& , at best at a tempera-
ture bet~een 80 and 150C, and if desired under pressure as well as at a pH
value of 4 to 10, preferably of 6 to 9. As solvents there are used dimethyl-
formamide, alkylglycols, for example ethyleneglycol-monomethyl or -monoethyl
ethers, lower alkanols, for example methanol, ethanol or butanol, or mixtures
of these solvents, mixtures of these solvents with water, preferably only
~ater.
Among the processes introducing ~Rt~r~salubilizinggroups into a
~enzoxanthene or benzothoxan~hene-imide derivative in analogy to the above-
mentioned process b) the following special variants of the process may be
pointed out:
b.-l) Conversion of a compound of the formula (10)
R3 o
Rl ~ { B ~ ~D2n
~ ~J Clo)
- R2 ~4
. ~herein Rl, R2, R3, R4, B, D and n have the meaning indicated for the formula
Cl), into a compound of the formula (1), wherein W stands for the sulfate
2Q group and m = 1, by reaction with sulfuric acid, preferably concentrated sul-
~uric acid, at temperatures of from 0 to 40C, preferably at room temperature
C15 - 25C).
.
-- 7 --
- ~,'~
,
' , '' ' ,. ,. ' ', ' ' ',...... : ,
- . . : . :, .
' ' ' . - :. :: . :: : .: . : .
:. .'': ' '' '
. ~ . - , .
.
lQ70693
; In this esterification care has to be taken that there is especially
no local overheating to avoid sulfonation in the benzothioxanthene or benzo-
xanthene nuclei.
.-2) Conversion of a compound of the formula (10) into the phosphato
compound thereof with concentrated phosphoric acid or polyphosphoric acid at
temperatures between 80 and 200C, preferably between lOO and 150C.
Among the compounds prepared in paragraph b,-l) and b.-2) of the
formula ~1) those are preferred in which n is zero and B is an alkrlene
; radical having 1 to 6 carbon atoms, especially a radical of the formula -CH2
or CH2-CH2- or an aromatic radical, especially the benzene radical (phenylene)
which may be substituted by alkylene radicals, as for example the radical of
the formulae
-CH2 ~ CH - or - ~ - CH2-
b.-3) The conversion of compounds of the formula ~ll)
R3
Rl ~ N (CH2)q OH
~Jo ~Il)
R2 R4
,~
into compounds of the formula ~12~
, .
.' ' ' ~, '--Q`; ~ ~
~ 8 -
, . . .
. ' ,
.
.
~. .
1070~93
R3
Rl ~ N - (CH2)q-0- Al- Ar -S03H
X ~ ~ (12)
in hhich X, Rl, R2, R3 and R4 have the above meanings, q stands for an integer
af:l.to 6, Al for a sulfonyl or carbonyl group and Ar is an aromatic radical,
~or example a phen~lene or naphthylene radical, by means of aryldisulfo-
monochlorides or -sulfochlorides of arylcarboxylic acids, for example the
benzoic acid-3-sulfochloride, in pyridine.
In this reaction the sulfochlorides used of the aromatic carboxylic
acids react via a complex compound of the pyridine as carboxylic acid chlor-
rides.
lQ b.-4)Conversion of compounds of the formula ~13)
: R4
Rl ~ N - ~CH2) -NH-R5
~ ~ ~ O (13)
~: R2 R3
into compounds of the formula (14)
.
:`
.
_ g _
. ~ .
.~
'~: . . ,.. .' '.' ~ "
': ' ' ' ' ': ~' ' ~ ' , : ' " '. ' ': '
1~70~i93
' Rl 3 ~ N - (CH2) -N -S02-Ar-S03H
R5 ~14)
. R2 R4
. in which X, Rl, R2, R3, R4, Ar and q have the above meanings and R5 is
hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably the methyl
or ethyl group, by reaction with aryldisulfomonochlorides, in which process
the formation of amide is carried out in known manner in an organic solvent
andtor water in the presence of an acid-binding agent.
b.-5) Conversion of compounds of the formula (15)
; R
R1 ~N - (CH2)q~ COC1
1~) ~ ~15)
R2 4
into compounds of the formula (16)
.'. O
R1 ~<~1N - (CH2) -CO-IN-R-SO3H
0 5
.. R2 R4
"..~
-- 10
. ,
~' ~
,
~ ' ,
~070693
wherein Rl, R2, R3, R4, X, q and R5 have the above meanings and R is an al-
kylene radical having 1 to 6 carbon atoms, preferably the methylene radical
or the ethylene radical, or the radical of the formula
CH2~
by reaction in known manner, with an amine of the formula
R5 - NH - R - S03H,
wherein R5 and R have the meanings mentioned, in water and/or in an organic
solvent in the presence of an acid-binding agent.
To isolate the compounds obtained according to the different vari-
ants of the process described above the reaction mixture, if necessary (cf.
process b.-l and b.-2), is stirred with ice water in usual manner, and the
pH is adjusted to 5 - 7 with sodium carbonate solution; the novel compound is
subsequently salted out with sodium or potassium chloride, suction-filtered
and dried.
The dicarboxylic acids used as starting compounds and the anh~drides
thereof of the general formulae (2) and (3) as well as the imides thereof of
the general formulae (10), (11) and (13) and the carboxylic acids required for
preparing the acid chlorides (15) may be obtained for example according to the
process described in German Patent Specification no. 1 297 259 and in German
.~ 2Q Auslegeschriften Nos. 1 569 761 and 1 770 818. -
The novel compounds of the formula ~1) have proved excellentl~ suit-
able as brilliant dyestuffs for dyeing and printing natural and synthetic
~ fibre material containing carbonamide groups, as for example wool, silk, syn-
- thetic polyamide fibres or polyurethane fibres. They yield on these materials
intense reddish to greenish yellow very brilliant dyeings, which partly have
an intense green fluorescence and show a fastness to light and to wetting
- 11 -
.
' : . : . : ' :: : . : .
, .
,
- : . : : : . - .
,:
1070693
which is unusually high ~or this class o~ dyestu~s. Their dyeings and prints
are generally distinguished by a very good fastness to light in a dry and wet
state, by good to very fastness to washing, also in the presence of perborates
or peroxides as well as other bleaching agents, such as hypochlorite, as well
as ~y a good acidic and alkaline fastness to perspiration, cross-dyeing, pot-
ting, fulling, water, sea water, alkalis, acid and rubbing. These novel dye-
stuffs also have a good absorption capacity with the fibres mentioned above,
a good color build-up and accordingly, a high tinctorial strength. The dye-
ings obtained with these dyestuffs are furthermore characterized by a very
good evenness; they provide even dyeings on texturized polyamide material.
It may also be pointed out that the novel dyestuffs have a very
good solubility in water, even in cold water, that they cause no or only an
insignificant blocking when dyeing in dyestuff mixtures, that they show a
good resisting property in the dyeing of mixed fabrics, especially at the
higher temperatures of about 100 to 230C necessary for example for the
thermofixation process, and that their aqueous dyestuff solutions, padding
-I liquors and printing pastes have a good viscosity property and a small sensi-
tivity towards electrolytes.
~1
The dyestuffs are above all superior to the dyestuffs of next com-
!.1 2Q parable structure from German Offenlegungsschriften Nos. 2 017 764 and
2 150 879 in respect of various tinctorial properties and fastnesses to use
and to processing, for example absorption capacity, color intensity, the even
~ dyeing of texturized polyamide containing differently drawn fibre moieties,
;~ fastness to alkalis and fastness to alkaline perspiration. On the fibre ma-
terial mentioned, some of these dyestuffs also provide in mixture with suit-
able blue dyestuffs very brilliant green shades having a very good fastness to
- light and to wetting.
An~ther advantage o~ the novel compounds is their technically easy
` - 12 _
. - ~
,.
.
:
- ~ 1070693
preparation. Starting from the benzoxanthene or benzothioxanthene-dicarboxylic
acids prefera61y used, or the anh~drides thereof having the general formula
C2) or (3) the compounds of the invention are obtained by reaction with the
amine of the general formula ~4) in only one reaction step; the novel compounds
are generally obtained with a very good yield and a very pure form. Moreover,
this reaction may be carried out in water.
Among the novel compounds those are particularly interesting in
~hich the individual radicals of the formulae having the general formula ~1)
have the following meanings: Rl or R2 or R3 is a meth~l or methoxy group,
the other two, each are hydrogen atoms, and R4 is hydrogen, or Rl, R2, R3 and
R4 are hydrogen each, X is oxygen or sulfur, the entire radical of the formula
~ B - (D)n ] forms an alkylene radical having 1 to 6 carbon atoms, prefer-
aBly two carbon atoms, or a radical of the formula
~ alkylene-,
- NH ~ , - NH ~ , .
- alkylene ~ , - alkylene alkylene-,
- alkylene - 0 - C0 - ~ W
; or
~alky~lene - C0 - N - alkylene-
alkyl
w~erein alkylene is an alkylene radical having 1 to 6 carbon atoms and alkyl
is an alkyl radical having 1 to 4 carbon atoms, preferably the methyl or ethyl
radical, W stands for the sulfonic acid group, for the sulfato, phosphato or
thiosul~ato group, and m is 1 or 2.
- 13 -
.: '': ~ : :
: ~. ,: ' .,
.
'' ~070693
A particularly~ ad~antageous and pre~erred variant thereo~ are the
compounds of the formula (1), wherein Rl, R2, R3, R4 and X and W have the
above meaning just mentioned, n is zero, m is 1 and B has the meaning men-
tioned for the formula ~1), but is especially a phenylene or naphthylene
group ~ith one or t~o terminal alkylene radicals having 1, 2 or 3 carbon atoms,
preferably the radical of the formula
" ~ or ~ c~2- ~
especially preferred for B is an alkylene group having 1 to 6 carbon atoms,
; having preferably 1, 2 or 3 carbon atoms.
' 10 ~specially excellent representatives of this class of compounds,
N~ich may be favorably synthesized are compounds corresponding to the general
formula C17~
~,~
.- O
. ~ N - B - W
~ ~ o ~ (17)
t
.~
~herein B stands for a radical of the formula
~ -CH2 - CH2 -, -CH2 - CH2 CH2 ~ 2
;: and W ls the thiosulfato or phosphato group, especially the sulfo or sulfato
gr~up .
The ~oll~ing Examples illustrate the in~ention, Parts and percent-
ages are By~ ~eight unless stated other~ise.
14 ~
. .
; ~
-- 1070693
EXAMPLE 1:
.
30.4 ~arts o~ benzothioxanthene-3,4-dicarboxylic acid anhydride were
suspended in 330 parts o~ dimethylformamide and refluxed for 8 hours together
with a solution of 14.5 parts of 2^amino~ethane-sulfonic acid and 7.8 parts of
potassium carbonate in 180 parts of water. A~ter cooling to room temperature
200 parts of a 15% potassium chloride solution were added until the imide com-
pound had completely precipitated. After some time the whole was suction-
filtered, washed wi~h a 10% potassium chloride solution and dried at 100C.
A~out 47 parts of benzothioxanthene-3,4-dicarboxylic acid-N-~-sulfethyl imide
o$ the formula
:' O
,. ~ N-CH2-CH2-S3H
~ ~S~ ~ '
were obtained in the form of the potassium salt. This novel compound dissolves
in water with a yellow color and provides according to usual dyeing processes
on wool and polyamide brilliant golden yellow dyeings having a good fastness
to light and to wetting.
EXAMPLE 2:
32 Parts of 10-methoxybenzoxanthene-3,4-dicarboxylic acid anhydride
~^ere introduced into a solution of 13.1 parts of 2-amino-ethane-sulfonic acid
and 5.3 parts of sodium carbonate in 500 parts of water and heated, while
stirring, in the pressure autoclave for 6 hours at 140C. After cooling the
i~i~de compound obtained was completely precipitated with 40 parts of sodium
chloride, suction-filtered and washed with a 10% sodium chloride solution.
- 15 -
.` ` ~,~,
':
.
.. ~ ,.
: .
.. ..
. .
.; . .
': :
1070693
~ After drying 43 parts of a compound were obtained which had in form of the
: free acid the following formula:
H3C0 ~ ~ 2-CH2-SO3H
~or an easier use as dyestuff the compound was ground. It dis-
! solves in water with a yellow color and a green fluorescence and is excellent-
ly suitable for dyeing and printing natural and synthetic polyamides, whereby
very ~rilliant greenish yellow shades were and are obtained.
EXAMPLE 3:
15 Parts of 9-methyl-benzoxanthene-3,4-dicarboxylic acid anhydride
~ere suspended in 180 parts of monoethylglycol and heated for 6 hours to 140C
in a stirring autoclave together with a solution of 7.5 parts of 2-amino-
ethane-sulfonic acid and 5.2 parts of sodium bicarbonate in 90 parts of water.
After cooling the imide compound thus prepared was salted out with a saturated
sodium chlsride solution, suction-filtered, washed and dried. About 21 parts
of a compound wereobtained which corresponds in form of the free acid to the
general formula
, O
N-CH2-CH -S0 H
,~ /` ~O
'' /~~
H3C
.. , ~.
~ ~` - 16 -
--` 1070693
It provides on wool and synthetic polyamide dyed according to pro-
cesses usual ln technique, very brilliant greenish yellow dyeings having a
very good fastness to use.
EXAMPLE 4
In analogous way as described in Example 2, 32 parts of 6-methoxy-
benzoxanthene-3,4-dicar60xylic acid anhydride were reacted with 13.7 parts of
2-amino-ethane-sulfonic acid. After salting out and washing with a 10% sodium
chloride solution, about 43 parts of a compound were obtained which had in
~crm of the free acid the ~ollowing formula
- , .
~ 2 2 3
:-10 ~0~'~
~ OCH3
: .
~ ith this compound dyeings of a brilliant rellow color were and are
obtained on synthetic polyamide fibre materials according to usual dyeing pro-
cesses.
EXAMPLE 5:
29 Parts of benzoxanthene-3l4-dicarboxylic acid anhydride were
: suspended in 450 parts of monoethylglycol and stirred with a solution of 19
parts of 2-aminoethyl-thio-sulfuric acid and 13.5 parts of sodium bicarbonate
in 160 parts of water for 7 hours at 95C. Then the whole was cooled to 50C,
and 550 parts of a 15% sodium chloride solution were added. The imide pre-
cipitated was suction-filtered, washed with a 5% sodium chloride solution,
dried at 100C and ground. About 48 parts of a compound were obtained which
correspond~ in the form of the free acid to the formula
~. - 17 -
: ~
:
.
, ' ' ~ ,
70693
,
~` N-CH2-CH2~S~sO3H
,~bo
: o
It provides on wool and polyamide brilliant greenish ~ellow dyelngs
having a good fastness to use.
EXAMPLE 6
17.3 Parts of 2-aminoethanol-sulfuric acid ester were dissolved
~ith 23 parts of sodium bicarbonate in 180 paTts of water, then 250 parts of
dimethylformamide were added and 32 parts of 10-methoxybenzoxanthene-3,4-
dicarboxylic acid anhydride were introduced. The suspension was stirred for
8 hours at 95C and at a pH value of 7 to 7.5. When the reaction was finished,
10 the imide obtained was precipitated with 200 parts of a 15% sodium chloride
solution, suction-filtered, washed with a 10% sodium chloride solution, dried
at 80C and ground. About 43 parts of a compound were obtained which has in
form o~ the free acid the formula
: O
~ N-CH2-CH2-O~O3H
H3Co ~
., ,
~t shows an orange yellow color. It provides on wool and polyamide
~i~bres greenish yellow very bTilliant dyeings and prints, having a good fast-
- 18 -
' ~ .
. ,.
- ' ,
: ~70693
ness to use according to dyeing and printing processes usual in technique.
EXAMPLE 7:
8.5 Parts of 10-methoxybenzoxanthene-3,4-dicarboxylic acid-N-~-
hydroxy-ethyl imide were introduced into 90 parts of polyphosphoric acid and
slowly heated to 140C while stirring. StirTing was continued for 8 hours at
this temperature. Then the reaction mixture was poured into ice and the phos-
phato compound obtained was salted out with potassium chloride and suction-
filtered. The moist filter cake was stiTred in water and neutralized with
potassium carbonate. After clarifying filtration of the solution and spray-
drying, about 9.2 parts of the compoùnd o~ the formula
:
O
H3C(1 ~ I CH2-CH2-OPO~OH)2
'
~ere obtained as potassium salt. It provides on synthetic polyamide a very
Brilliant greenish yellow dyeing having a very good fastness to use.
EXAMPLE 8
14.5 Parts of phen~lhydrazine-2,5-disulfonic acid were dissolved
with 2.8 parts of sodium acetate and 9 parts of sodium carbonate in 40 parts
o~ ~ater. Then 200 parts of monoethyl glycol were added and 16 parts of 10-
methoxybenzoxanthene-3,4-dicarboxylic acid anhydride were introduced; the
suspens~on ~as heated ~or 12 hours at 140C in a stirring autoclave. After
co~ling the reaction mixture was diluted with 1000 parts of water and filtered
~ ~ . ~ - 19 -
k ~, ~, .
',~
';
' ' `
1070693
hot ~ith addition o~ kieselguhr. The hydrazide compound obtalned was pre-
cipitated ~rom the filtrate by sodium and potassium chloride, wash0d with
saturated sodium chloride solution and dried at 100C. About 27 parts of the
compound of the formula
0 SO3H
H3CO N-NH ~
~ere obtained as potassium and sodium salt. According to technically usual
dyeing and printing processes it provides a brilliant yellow color on syn-
thetic polyamide fibres.
EXAMPLE 9:
The reaction of 16 parts of 10-methoxy~benzoxanthene-3,4-dicarboxylic
acid anhydride ~ith 20 parts of the sodium salt of the 4-aminobenzyl-sulfonic
acid according to the conditions mentioned in Example 8 provided about 25
parts o~ the compound of the formula
O
H3CO ~ N ~ ~3 CH2-503H
. o~
as potassium or sodium salt. rt y~ields on synthetic polyamide ~ibre materials
ver~ brilliant yello~ dyeings having a very good ~astness to light.
~ 20 -
., .,.;~ .
c~,. ^ ,
`
. . . .
`
, , . . . ' ' '. ' '
.
1~70693
.. . .
EXAMPLE 10:
Into a mixture of 5 parts of the hydroxy compound of the formula
O
~ N CH2_cH2_oH
and 50 parts of pyridine, 7 parts of benzoic acid-3-sulfochloride wereintro-
duced while stirring at 20 - 30C during 30 minutes. Stirring was continued
~or one hour at 30 - 40C and for 2 hours at 40 - 50C, whereby a complete
dissolution took place. At 40C 50 parts of water were added dropwise and
stirring was continued for one hour at 60 - 70C. To precipitate the compound
formed, 200 parts of a saturated sodium chloride solution were added at 25C;
lQ the precipitated product was suction-filtered, washed with saturated sodium
chloride solution and dried at 60C in vacuo. 10.4 Parts of a compound were
obtained which had in the form of the free acid the following formula:
O
-CH2-CH2--C ~ S03H
D
r
T~is dyestu~f provides on synthetic polyamide fibre material a
,,:
brilliant greenish yello~ dyeing.
- 21 -
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~070693
EXAMPLE 11:
To a mixture of 5 parts of the acid chloride of the formula
O
COC I
prepared from the corresponding carboxylic acid ~ith thionyl chloride, and150 parts of acetone, a solution of 4.5 parts of N-methyltaurine as sodium
salt in 50 parts of water was added dropwise while stirring, at 5 - 10C
within one hour. Then stirring was continued for 3 hours at 10 - 20C and
for 5 hours at 20 - 30C, the pH value being maintained at 6 - 7. After the
reaction 100 parts each of a saturated sodium chloride solution and potassium
chloride solution were added. The precipitate was suction-filtered. The
moist filter cake was washed with a saturated sodium chloride solution and
then stirred in 400 parts of water. After clarifring ~iltration o~ the solu-
tion and spray-drying 3.4 parts of the compound of the formula
O
~ ~ ~\rl N-CH2-CO- ~N-CH2-CH2-S03H
H3C ~ ~ ~ " ~ CH3
.' ~
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~ere o~tained as ~otassium/sodium salt. This d~estuff provides on synthetic
polyamide fibre material a brilliant greenish yellow color.
,.~
- 22 -
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