Note: Descriptions are shown in the official language in which they were submitted.
The present invention relates to an i.mproved process
for the manufacture of compounds of the formula ~.
OH O C ~
I 1 3 NH
R_~ ~r R ~
So2-cH2-cH2-oso3H So2-cH2-cH2-oso3H
~II) (III)
by the esterification and optionally hydrolytic ring cleavage,
starting from a compo~md of the formula
C~O
\l IH
~/ II)
R~
1~1 ~
: ~ '
2 2 2
,~ :
which is characterized in that the reaction is carried out
with 1 to 2 times the equimolar amount, relative to moles of
SO3, of 92 to 100 % strength sulfuric acid or of sulfur trioxide
or of sulfuric acid containing sulfur trioxide, optionally with
the subsequent addition of water, whilst mixing thoroughly.
: - 2 - ~
:
- : : - : .. :,:: . .: ~ :: : : :
.; : , : ; ; . , ,: ~, , , - , , ,:,: , . ~ - :,~
- :... :; . : .. :: . . . . . :.
HOE 76/I; 183
~LW~
In these ~ormulae (I), (II) and (III), R represents
hydrogen or a lower alkyl group, such as a methyl or ethyl group
and of these, in particular, the methyl group, or the nitro
group or a chlorine or bromine atom; the ~-hydroxy- or ~-sulfato-
ethylsulfonyl group is in the 5- positio~ or 6 position of
the benzoxazolone ring or in the 4~ position or 5- position of
the benzene nucleus of the aminophenol.
The manufacture of 2-amino-phenol-4~-sulfatoethyl
sulfone and -5-~-sulfatoethyl sulfone ~d of 5-~-sulfa-toethyl
sulfol~yl- and 6-~-sulfatoethylsulfonyl-benzoxazolone by the
process according to the invention is particularly preferred.
The compounds of the formula ~II) and (III~ are suitable
for use as precursors (diazo componentsj for the manu~acture oP
azo dyestuffs.
The conversion of compounds of the formula (I) into
compounds of the formula (II) with hydrolytic cleavage of the
oxazolone ring is in itself kno~. However, the method
described hitherto requires large excesses of sulfuric acid
which~ either during the working up of the esterification
produc-t of the formula (II) and during its isolation or during
' I ' ~ . .
:. ^ ^ : ^
1~9 8~1 HOE 76/F 183
- its further processing to dyestuffs, must be diluted with wa-ter,
neutral~ ed and separated off from the este~ification product
or from the dyestuffO Thus recovery of the sulfuric acid
is virtually excluded. In addition, the acîds, as such or
in the neutralized form as soluble sulfates, pollute the effluent.
Furthermore, the known esterifica-tion process has the
disadvantage that the compounds of the formula (II) are obtained
as solutions in sulfuri.c acid; however, these solutions are not
very suitable for storage, for example for fur-ther processing
oarried ou-t later.
Thus, according to German Pa-tent Specification 1,153,02
the esteri~ication o:E a compound of the formula (I) is carried
out with 6 times the equimolar amount of concentrated sulfuric
acid. After dlluting the sulfuric acid solu-tion with a
large amo~t of ice and water, the compound obtained of the
formula (II) is isolated as a solid by suction ~filtering off).
In this procedure, it is obtained in a yield of only 67 % of
theory; the rest remains in -the mother liquor, as does
the excess dilute sulfuric acid which must be neutralized for
the effluent~ However, the product which cannot be isolated
and -the sodium sulfate represent a considerable pollution of
the effluent.
Neutralization o~ the excess sulfuric aci.d wi-th calcium
carbonate and filtering off of the sparingly soluble calcium
sulfate, such as is described in Example 2 of German Patent
specification 1,153,029, indeed eliminates pollution of the efflu-
ent, but requires additional expenditure on labor and material;
29 furthermore, this method has the disadvantage that the gypsum
. - 4 -
: : ,. : . . , . , ~ :
~389~ ~ HOE 76/F l83
thus obtained must b~ dumped as unusable industrial waste.
Likewise, the pollution of the effluent is vel~ high
when aminophenol manu~actured by the known process is used
directly, after dilution with ice and water, for the manufacture
of an azo dyestuff (diazotization and coupling with the desired
coupling component and, if appropriate, metallization): the
dyestuff manufactured is isolated by salting out with sodium
chloride or potassium chloride, whilst the sulfa-te and a large
proportion of the chlorides remain dissolved. However, an
ef~luen-t-free isola-tion of the d~estuffs by evaporating or
spray-drying the dyestuff solutions ob-tained,without previously
separating off the sulfate~would lea~ to dyestuff po~ders which
are very weak in color and con-tain a high proportion of. neu-tral
salts and ~Ihich would scarcely be of interest for industrial
use.
There was thus an urgent need for an esterification
process which avoids these disadvantages and results in virtually
no pollution of the environment or subs-tantially less pollution
of the environment.
An improved process has now been found for the esteri-
fication of the abovementioned compounds of the formula (I)
to give their sulfuric acid semi-esters of the formula (II~
and (III), which is characterized in tha-t the reaction of a
compound of the formula ~I) is carried out with l to 2 times
the equimolar amount, relativetO moles of SO3, of 92 to lOO %
strength sulfuric acid or sulfurtrioxide or sulf.uric acid
containingsul~ur trioxide, preferably ~rith a content of up to
29 about 70, in particular from 15 to 65, % by weight of sulfur
: ' . - . .
' . ' ' . '
- . . . , ,,.. .. . : . ..
. ,.: .. .: .
.. , ~ . . .. ... ~ ..
:. .;: . . . . . .
~38~ HOE 76/F 183
.. ~
trioxide, whilst thoroughly mixing.vigorously, preferably in a
machine operating with a kneading action and effect hereinafter
ealled kneader.
The reaction temperature can be between ~10C and 180C.
As a rule, the temperature is regulated by means of the cooling
or heating jacket. of the reaction vessel or the kneader Depending
on the temperature and the mixing or kneading intensity as well
as the esterifying agent employed, the treatment time of the
reaction mixture in the kneader or mixing apparatus can be a few
1 0 -
_ minutes to several hours.
The process can be carried out in a si~ple manner by
~ either initially introducing one of the reactants
into the reaction vessel provided with an intensively operating
~ mixing device or into~lemachine operating with a kneading action
and gradually adding the second component to this, or by adding
both components simultaneously or as a mixture to this reaction
vessel or the kneader.
Purely to esterify the compound of the formula (I) to
give -the compound of the formula (III), oleum or sulfur trioxide
itself are preferably used as the esterifying agents; ho~ever,
the esterification can also be carried out with 92 to 100 %
~trength sulfuric acid at temperatures below 100C, appropriately
at 10 to 90C. The reaction and kneading time is about 5
minu-tes to 6 hours.
. The esterification of the compound of the formula (I)
with simultaneous hydrolytic cleavage of -the oxazolone ring
is appropriately effected by carrying out the esterification
29 by means of 9~ to 100 % strength sulfuric acid at a temperature
. 6 - ~ .
, 'I :' ,. ~' " ' :: ~", ." ,, '
HOE 76/F 183
from 100 - 180C, pre~erably at 120 - 160C. The reaction is
particularly advantageously carried out at a temperature between
120 and 160 C in thecourse of a reaction and mixin~, resPectivelv kne~g
time of 2 to 20 hours, which under these conditions, depends in
par~icular on the mixing, respectively kneading intensity applied,
which`in turn can depend on the type of machine.
A modification to this process for the manufacture of
compound (II) from compound (I) consists in first esterifying
the compound o~ the formula (I) in the manner indicated above
1~ and subsequen-tly, if the esteri~ication had been carried out
with 92 to 100 % streng-th sulfuric acid below 100C, increasing
the reaction temperature in the mixer or ln the kneader to
100 to 180C for the hydrolytic cleavage or, if oleum or sul~ur
trioxide was used as -the es-terifyinO agent, carrying out the
hydrolytic ring cleavage in the mixer or the kneader at l00 -to
180C by s-lowly adding water in an arnol~lt su~h that a 92 to
100 ~0 strength sulfuric acid is obtained. The sul~uric
acid used in the reactionswith the compounds of the formula (I)
is preferably employed as 95-98 % strength sulfuric acid, as
so-called monohydrate (100 % strength su]furic acid) or as
oleum. 1.0 to 1.5 times, in particular 1~1 to 1.5 times,
the equimolar amount, rela-tive tomoles of S03, of es-terif~Jing
agent are pre~erably used.
~ In order to improve the kneading action or the heat
transfer in the kneading mixture during the kneading process,
added inert adjuvants, such askieselO~uhr, talc or metal powder,
can also be co-processed and can then be separated off again
frGm the sulfuric acid s ~ -ester prepared of the formula
29
,' .
,
__., ......................... ~ .. . . . ..
, ~ " .: , ,
, , . ~. . : .
,, : . . .
~IOE 76/F 183
8~
(III) or (II), or from a dyestuff manufactured from this, by
simple filtration from an aqueous solution during the working
--- up or further processing of the kneaded material.
By machines which operate with a kneading action -there
are to be understood -those which are suitable for mi.xing, dis-
- 5 persing or homogenizing and which can process the liquid/solid
components wi-th one another, using high forces. In these rnachines,
the processing (kneading) takes place under high pressure in the
customary mannerinsucha~.~ythat~ ofthe machine running in the
s~ne direction or in opposite directions, preferably at differ-
ent speeds, such as cylinders, discs, rollers, closely meshing
toothed wheels and screws, mix the components with one another
under high pressure, if appropria-te with the applica-tion of
shearing forces. Such machines having a kneading action,
hereinafter called kneaders, are, in àddi.tion to actual kneaders
and extruders -themselves, also, for example, saw-toothed s-tirrers
(dissolvers), rotor stator mills, dispersers and roll mills.
These machines can operate discontinuously and also continuously;
a large number of them are known in the commercially available
form, Discon-tinuously operating kneaders are, for example,
twin-bowl kneaders, s-~ch as sigma blade kneaders, dispersion
kneaders and dispersion ram kneaders, and continuously operating
-kneaders are, for example, kneading extruders (for this, see
also Ullmanns Encyclopadie der Technischen Chemie, volume 1 (1951),
- pages 725-727; and Ullmanns Encyclopadie der Technischen Chemie,
4th edition, volume 2 (1972), pages 2~ and 292-299).
The reaction-mix (kneadinq product), both of the forrnula (II) and of
the formula (III) is worked up, after the esterifica-tion and,
. i~ appropriate, hydrolytic ring cleavage,in the reaction vessel
2~
-- 8
1~98~a~ HOE 7 6 /F 1 8 3
._.,
~kneader), in a manner which is customary and familiar to the
expert. It is advantageously effected by dissolving the
reaction mix in ~ater, whilst simultaneously neutralizing the
solution. The neutraliza-tion is preferably carried out with
sodium bicarbonate or sodium carbona-te. The neutral or ver-y
weakly acid solution is then evaporated to dryness or spray-
dried, if appropriate after separating off the abovemen-tioned
inert adjuvants, for example by filtering or cen-trifuging. In
this manner~ for example in the case of neutralization with the
aboyementioned sodium salts, the compound of -the formula (II) or
(-III) is ob-talned in the form of its sodium salt. Potassiurn
bicarbonate or potassium carbonate can correspondingly be used
for the neutralization. A further possibility for working
- up the reaction mix (kneaded mix) is to neutralize with calcium
1S carbonate, after dissolving in water, to filter off the calcium
sulfate which has formed and precipitated and to add sodium
oxalate or oxalic acid and sodium carbonate or bicarbonate to the
filtrate, to separate the solution in the customary manner frorn
-the precipi-tate ~ormed, for example by filtering or centrifuging~
, and then to spray-dry it. In this new esterification process
substantially lo~ver amoun-ts of gypsum are obtained than in the
processes known hither-to
- An outstanding and important advantage of the esterifica-
tion process, according to the invention, for ~e PreParatiOn of
the a~inophenol compounds of the formula (II~ is, however, that
working up of the end product is not necessary at all In
fact the reaction products leave the kneaders in the
form of powders or crumbly or small lumps or asa plastic
2~
_ g _
; ~ . . .
. . ~ ,. ..... .. .... . . .... .
. : . . . ~ :.,
_OE 76/F 183
~g~9B9~l
cornpositîon; they can be easily stored and transported in this
form Using them, an easy, ef~luent-ree and non-pollutinO
urther processing ls p~ssible to qive fibre-reactive azo dyestuffs
of the formula (I~r)
OH
1~ - N = N ~ . (IV)
" . ~ :
S2 C1~2 ~ 2 3
in which R has the abovementioned meaning, the ~-sulatoe-thyl-
sul.~onyl group is in the 4-position or 5-position of the diazo
component and K represents the radical o~ a coupling component
which can also contain an azo grouping, in par-ticular -to give
metal compl.e~ compounds of these dyes-ku~fs,
since the process products of the formula (II) resul-ting from the
esteri.~ication process according -to the inven-tion are obtained
with a degree of es-terification of 95-100% and in high yield bu-t,
surprisingly, in addition also in a higher quality than rom
known processesO Accordingly, the me-tal complex dyestuffs
obtainable from the process products of the esterification pro-
cess according to the invention are o~ excellent ~uality, the
shades of the dyeings and prints produced with them on cellulose
~iber materials are`of high puri-ty, and in addi-tion they are
obtained in high yield, calculated relative to -the starting com-
pound o~ the above ormula (I~.
Below 50C, the kneaded mix is usually obtained as a
powder when 1 to 1.5moles o~ esteriying agent are employed per
' ~ . . " '
~ ~;
, ... .... _ ., .. _
. .. . .. . . . . . .. ..
3L IIOE 7 6 /F 18 3
.
mole of compound o~ the formu'a ~I), and as a powder or in the
plastic form when l 5 to 2 moles of esterifying agent are used
per mole of compound of the formula (I). The kneaded mix
obtained according to the process can ke stored and -transported,
preferably ~'n the form of a'powder, without problem in dru~ns,
so that further processing, for example to give dyestuffs, can be
carried out at a time ànd place independent of -the esterification.
In further processing to give azo dyestuffs, the kneaded
mix is diazotized in an aqueous solu-tion which is acid to Congo
Red, it optionally being possible, depending on the amount of
esterifying agent employed in the esterification process, -to dis-
pense, partially or completely, with a fur-ther addition af acid.
The diazo-tization is carried out in a known and customary manner,
as is also the subsequent coupling with a coupling component of
the f'ormula EI-K, in which K has the abovementioned meaning, after
adjusting the pH~to an appropriate value, with the formation of a
dyestuff of the abovementioned formula (IV), which in turn can be
converted in an advan-tageous manner into a metal complex compound,
in particular a copperS cobal-t or chromium complex dyestuff, in
the same reaction medium using a me-tal-donating agent.
Because of the relatively low con-tent of sulfate, arising
` from the esterifica-tion, in -the dyestuff solution thus manu-
~actured, it is not necessary to separate out the dyestuffs by
salting out with sodium chloride or potasslum chloride and then
to filter them off, but the weakly acid to neutral dyestuff solu-
tions can, in an advantageous manner, be evaporated to dryness
directly or subjected to spray-drying directly.
' 29 Dyestuff powders of high tinctorial strength which
.
~,' ,--' - 11 -
.
- : . ~ . . ~ .
- ,~., . ., . . ~........ . -
~ HOE 76/F 183
correspond, in their properties, to the products manufactured in
a kno~ manner, but which in general. surpass these with respect to
the degree of esterifi.cation of the ~-hydroxye-thylsul~onyl group,
the conten-t of dyestuff of the formula (IV) or its metal complex
compound, the tinc-torial streng-th1 the solubility in water and
the dyestuff yield, are thus ob-tained in very ~ood yield and in
excellent quali~y and purity.
Because of the good solubili-ty of the dyestu~f, the d~re-
s-tu~f solutions ob-tained can be employed directly for dyeing
; 10 purposes, i~ appropria-te after additionally concen-trating to a
smaller volume.
The present invention -thus also relates -to the simplified
manufacture of fiber-reactive azo dyestuf.~s using -the process
products of the formula (II), obtainecl in the esterification
~5 process according to th~ invention, whi.ch is characterized i.~l-tha-t
the reaetion m~x (kneaded mix) is emplQyed directly, without prior isolation
of eompound (II), as the diazo component~ ;f appropriate dissol.ved in ~ater,
and diazotized in aeeordanee with customa1^y proeesses, the diazotization
produet is coupled with a coupling component, after adjusting the pH to a
value appropriate for azo coupling, and the azo dyestuff thus
obtained is op-tionally metallized, without prior isola-tion, ~ld
then isolated by spray-drying or evaporating
The examples which follow serve to illus-trate -the subject
of the invention. The parts by weight given in them bear
-~ 25 the same relationship to parts by volume~as the kilogram to the
liter.
.~ a) 3,866 parts by weight of 6-(~-hydroxyethylsulfonyl)-
2g
- 12 - .
; , -, ; . ,
HOE 76/F 183
~t~
zoxazolor.e (9~ pure~ ~te. a ~oduct contq~ ~ 94.4 % of ~e pure
oxazolone c~und,the resi~ual po~tion ~eing ~lelec~ol~e~ ~ch as sodium
chloride or ~ium sulfate~ were initially ~trod~ced as a dry po~der into
a c~rcially available dispersion ~.eader (for ex~le from~essrs. W~er &
Pfleiderer, Stutt~t~Feuerbach), one kneading ~ of~lch ran at a s~
of 29 rpm and the other knead~g arm of whIch ran at 21 rpm, ~d were heat~d
to 110-120 C by means of jacket heat~ng ~,gao parts hy weight of 98 %
.. . .
strength sulfuric acid were -then allowed to r~ in in the course
of lO minutes, whilst the machine was running, and the reac-tion
mixture was worked in the rvnning kneader .~or about 14 hours at
140-150C. An initial foam formation was suppressed by add
ing a small amount of a co~nercially available silicone anti-
foaming agent dropwise. A dark, pasty composition was formed,
which on cooling to room temperature f.irst became pu-tty-like and
then crys-talline and finally gave a greenish-tinged grey powder.
The 1~neader was then emptied. 4,960-parts by weigh-t of 2-
amino-l-hydroxy-5~ sulfatoethylsulfonyl~-benzene (86% pure),
correspondlng to a theoretical yield of 95.7%, ~ere obtained as
a powder.
b) 2.0 parts by weigh-t o~ the kneaded mix were stirred, at
O to 5C, in-to a mixture of 8 parts by volume o~ water and 2 parts
by weight of ice, whilst simul-taneously adding about 0.7 part by
weight of sodium bicarbonate in portions. The pH value of
the aqueous solution thus obtained was about 4.5; -the solution
was clarified by filtration and evaporated to dryness in vacuo at
60 -to 65C. After grinding, 2.1 parts by weight of a
yellowish white powder were obtained which contained, in addition
~- to 9% by weight of sodium sulfate~ the pure compound of the formula
2q
. ..
13 -
~11
~nHz
O21S
CH -CH -OSO H
in the orm of its sodium salt.
Example 2
3,866 parts by weight of 5-(~-hydroxyethylsulfonyl~-benzoxazolone
~94.4% pure) were initially introduced as a dry powder into a commercially
available dispersion kneader. 1,607 parts by weight of 65% strength oleum
were allowed to run in in the course of 20 minutes~ whilst the machine was
running. The tempera~ure-was kept below 100C by jacket cooling. Af~er 2
hours, the putty-like reaction composition, which essentially contained the
compound of the formula C
O~ \
¦ NH
~/
O S
2l
CH2-cll2-oso3H
',,~
was heated up to l25-130C by steam jacket heating. 250 parts by weight of
water were added dropwise in the course of 2 hours; foam formation was sup-
pressed by a silicone anti-foaming agent. After the water had been added, the
reaction temperature was increased to 145-155C and the composition was left
in the running machine at this temperature for 20 hours. Thereafter, the
contents of the kneader were cooled to room temperature, whereupon they became
solid and turned into a powder. 5,100 parts by weight of 2-amino-1-hydro~y-5-
, - 14 -
- .
- . :
" , ;,:
1 ~ 89 ~!~
:
ExampleStarting compound ~nd produc~
c~O ::~
O ~ \ OH
Br ~ Br ~ ~ ~ 2
~ -CH -CH -OH SO2-CH2-CH2-OS03H
o_~ C~ O~H ",
~_ ~NH2
S02-CH2-CH2-oH S02-CH2-CH2-OS03
C~ OH
O2N ~ NH O2N ~ H2
S02-CH2-CH2-oH so2-cH2-C}~2-so3H . .
. .
; Example 8
', 69 parts by weight of the kneaded mix manufactured under Example la ~::
were dissolved in ~a mixture of 300 partS by volume of Water and 150 parts by
~' weight of ice and diazotized with 40.1 parts by volume of 5 N sodium nitrate
: .
' solution, After the diazotization reaCtion, a slight nitrite excess was
,
; destroyed after subsequently Stirring for 15 minUtes with a little amidosulfonic
~ acid. The yellow diazonium salt solution was added to a solution, adjusted to
;~ neutral, of 76 parts by weight of 1-amino-8-hydroxy-4~6-dlsulfonic acid ~84%
strength) in 300 parts by volume of Water. The pH was adjusted to 6 to 7 With
anhydrous sodium carbonate and kept at this value until the coupling had ended
- 16 ~
: ~'
.. ..
~no further ~iazonium salt could be detected). 50 par~s by weight of crystal-
line copper sulfate were then added and the pH value was adjusted to ~.5 to
5.0 with 50 parts by weight of crystalline sodium acetate and with sodium
carbonate. The reaction solution was subsequently stirred at room temperature
for 1 hour, then clarified~ with the addition of 10 parts by weight o kiesel-
guhr, and evaporated at 50 to 60C.
The residue was ground; 240 parts by weight of a blue-black dyestuff
powder were obtained, which contained 63% by weight of the dyestuff of the
formula ~ Cu
O ~ O NH2
~ 10 ~ ~
- CH2-2S Na 03S S0 Na
- I 2 3
.' OS03Na
;~ in the presence of an agent having an alkaline action, this dyestuff gave deep,
,~:
:
navy blue dyeingsand prints of very good fastness to light and wet processing
on cotton and other cellulose fiber materials by the known customary dyeing
proceaures for reactive dyestuffs.
~`; A dyestuff powder of the same dyestuff content and of equally good
quality is obtained when the clarified dyestuff solution obtained during the
manufacture is spray-dried instead of evaporated.
Example 9
70 parts by weight of the kneaded mix, manufactured analogously to
Example la, of the compound from Example 2 were dissolved and diazotized as
described in Example 8. The solution of the diazonium salt was coupled with
136.5 parts by weight of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic
, -
:: : ~ .. , - . : :.: ... . ..
acid ~53% strength) at a pH value of 6 to 7. 50 parts by weight of chrome
alum were added to this solution of the azo dyestuff formed, having in the form
of the free acid, the formula
OH HO N~l-CO-CH
H03S S03H
2
2 2 3
without intermediate isolation~ and the mixture was adjusted to a pH of 5.3
to 5.7 with crystalline sodium acetate. The reaction mixture was then boiled
under reflux for about 10 hours until no further metal-free dyestuff could be
detected in the chromatogram. The solution of the 1:2 chromium complex dye-
stuff formed was clarified, with the addition of lO parts by weight of kiesel-
guhr, and thereafter spray-dried. A blue-black dyestuff powder was obtained
which gave, in the presence of an agent having an alkaline action, strong,
clear, navy blue prints and dyeingsof very good fastness to light and wet
processing on cellulose fiber ma~erials, when fixed according to the customary
and known dyeing and printing processes for reactive dyestuffs.
Examples 10 to 18
In addition, as can be seen from the tabular Examples which follow,
the metal complex dyestuffs indicated in the table could be prepared from the
compound of the formula ~II) obtained according to the process of the invention
without intermediate isolation of the diazo component itself. In fact, if
the process is carried out by applying, in the general sense, the procedures
indicated in Example 8 or 9 in such a way that the sulfato compounds of ~he
- 18 -
. . .
:. . : ~ .
.. c
- . . . ~ -
891 ~
formula ~II) indicated in the following Examples, are first diazotized, the
diazotization product is then coupled in the customary manner with the cor-
responding coupling component indicated in the Example, the azo compound form-
ed is subsequently converted into the corresponding metal complex compound by
treatment with a copper-, cobalt- or chromium-donating metallizing agent and
the dyestuff thus obtained is isolated by evaporation or spray-drying, dye-
stuffs (dyestuff powders) are obtained which yield deep dyeings and prints
on cotton in the color shades indicated in the Examples, which are fast to
light and wet processing.
The compounds (A) and (B) stated in the Examples, represent the com-
pounds of the following formulae
. ~ .
; OH OH
NH2 ~ - NH~ ~
SO -CH -CH -OS03H o2S ;:
CH2-CH2-OSO3H
~ ~A) ~B)
'.:
- 19 -
Ex- Compound Coupling component Metal Color shade on
ample of the cotton
formula II
(A) HO3~ ~ SO3H opper bl~ish-tinged red
11 (B) COOH Copper yellowish-tinged
I _ brot
12 (A) ~ H ro c ~ opper red-violet
13 ¦ (A) HO ~ = h ~ opper bro~
~ ~IO NH-CO-CH3
14 (B) ~ Copper ~ violet
- 20 -
, '17 r ~
:.' ' ~ '' ~ ,"
'.' 1 `~ `; ', ~ ,
~g~
Ex- Compound Coupling component Metal Color shade on
ample of the cotton
formula II _ _
lS~ (B~ 1 ~3 c~pp r claret
(~\) J __~ CH3~ Copp r yellow
17 ~ ( 3) ~ ~ )~NH2 Chrom um ~ grey
18 ~A) ~ Cobalt black
~ /~ SO 3H
Example 19
3~866 parts by weight of 6-~-hydroxyethylsulfonyl)-benzoxazolone
~94.4% pure) were initially introduced as a dry powder into a dispersion
kneader. 1,607 parts by weight of 65% strength oleum were allowed to run in
in the course of 20 minutes, whilst the machine was running. The reaction
temperature was kept at 100C for a reaction time of 90 minutes. After cooling,
- 21 -
-
98~
5,400 parts by weight of a product were obtained, which contained 88% of the ~.
compound of the formula
C~
~ -NH
2l
2 2 3
~ which compound had been ob~ained with a degree of esteri-fication of 98%.
:~ 2.0 parts by weight of the kneaded mix thus obtained were stirred, at
0 to 5 C, into a mixture of 16 parts by volume of water and 4 parts by weight
of ice, whilst simultaneously adding about 0.7 part by weight of sodium car-
bonate in portions. The pH value of the aqueous solution thus obtained was
5-5.5; the solution was clarified by filtration and evaporated to dryness in
vacuo at 60 to 65C. After grinding, 2.1 parts by weight o~ a yellowish whi.te
powder were obtained which contalned, in addition to 8% by weight of sodium
sulfate, the pure compound of the formula
C~O
o2sl
CH~ - CH2-OSO3H
in the form of its sodium salt.
:
TIIE EMBODIMENTS OF THE INVENTION IN WIIICH AN ~XCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process or the preparation of a compound of the formula
OH O _ C
n ~ or R - ~
SO2-CH2-C~12-OSO3H SO2-CH2-CH2-Oso3H
~II) (III~
in which R is hydrogen, lower alkyl~ nitro, chlorine or
bromine, and the ~-sulatoethylsulonyl group is in the
5-position or 6-position of the benzoxazolone ring or in
the 4-position or 5-position of the benzene nucleus, by
esterification and optionally hydrolytic ring cleavage,
starting from a compound of the formula
o
0~~\
~ NH
R ~
~ ' .
so2-CH2-cH2~o~l ;
:in which R has the abovementioned meaning and the ~-hydroxyethyl-
sulfonyl group is in the 5-position or 6-position of the benzoxazo-
lone ring, characterized in that the reaction is carried out with
1 to 2 times the equimolar amount, relative to moles of SO3, of
92 to 100% strength sulfuric acid or of sulfur trioxide or of
23
.
