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New Reactive Dyes.

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Iaudanosoline methiodide (70), for example, which
leads smoothly to aporphine (71) [63] may be justifiably assumed [64] to be a free-radical reaction.
On the other hand, the dehydrogenation of laudanosoline (72), in which the nitrogen is not quaternized,
proceeds smoothly with the formation of the dibenzotetrahydropyrrocoline derivative (731, whose trimethyl
ether occurs in nature as cryptaustoline [65]; it is cer[63] B. Franck, G. Blaschke, and G. Schlinglqff,Tetrahedron Letters 1962, 439.
1641 B. Franck andG.Schling/aff,LiebigsAnn.Chern. 659,123(1962).
1651 J. Ewing, G. K. Hughes, E. Ritchie, and W. C. Taylor, Nature
(London) I69, 618 (1952); Austral. J. Chem. 6, 78 (1953).
tainly justified to include this reaction among the
quinone additions [66,67].
W e are sincerely grateful to all those who habe helped us
in word and in deed, with encouragement and criticism,
and to the Deutsche Forschungsgemeinschaft, the Fonds
der Chemischen Industrie, and to Schering A.G.
Received, December 2nd. 1963
[A 360/159 IE]
German version: Angew. Chem. 76, 313 (1964)
Translated by Express Translation Service, London
[66] R. Robinson and S. Sugasawa, J. chem. SOC.(London) 1932,
789.
[67] C. Schopf and K. Thierfelder, Liebigs Ann. Chem. 497, 22
(1932).
New Reactive Dyes
BY DR. K. G. KLEB
LABORATORIUM DER ZWISCHENPRODUKTEN-ABTEILUNG
DER FARBENFABRIKEN BAYER AG. LEVERKUSEN (GERMANY)
AND DR. E. SIEGEL AND DR. K. SASSE
WISSENSCHAFTLICHES HAUPTLABORATORIUM
DER FARBENFABRIKEN BAYER AG. LEVERKUSEN (GERMANY)
Dedicated to Professor ff. Bredereck ox the occasion of his 60th birthday
Two new groups of reactive dyesti@ have been developed. One group (Leva$x@ dyes)
comprises compounds which contain -SO2NH- CH2 -CH2-OS03 H or -CH2-N(a1kyl) CH2-CH2-OS03H as reactive groups. The dyes of this group react with cellulose fibers
to form cellulose ethers, e.g. R-S02NH-CH2-CH~-O-cellulose.The substances in the
second group (Levafix-E@dyes) consist of the amides formed from 2,3-dichloroquinoxaline6-carboxylic acid and dyestuffs containing primary or secondary amino groups.
Introduction
(b) the Levafix-E d y e s containing 2,3-dichloroquinoxaline-6-carboxylicacid bound as its amide as the
reactive group.
The development of new reactive dyes requires solutions
to problems which fall essentially into two categories :
1. The discovery of reactive systems which are suitable
for incorporation into dyestuffs and which react efficiently with the substrate to be dyed under the conditions of textile dyeworks.
2. The combination of the reactive systems with dyestuffs, either already known or new, to give reactive
dyes of high fastness.
The first problem is the more difficult one, since the
reactive group both prescribes the type of dyestuff and
largely determines the properties and scope of application of the dyes obtained with it.
Our work has led to two groups of dyestuffs:
(a) the Levaf ix dyes containing the reactive group
-S02-NH-CHr-CH2-OS0,H
and
408
or -CHr-N-CH2-CH2-OSO,H,
R
1. Reactive Dyes with Sulfatoalkyl Groups
Activated by Neighboring Groups [*I
In 1940, H. Schweirzer and 0. Bayer described dyes
containing N-(P- or y-chloroalky1)sulfonamido groups
which imparted colors to wool [l] more wash-fast than
comparable deyings. The action of alkalies on N-(Pchloroalky1)sulfonamides ( I ) readily produces N,Nethylenesulfonamides (2) [2], which react with primary
or secondary amines - probably also with the amino
groups in wool - to effect alkylation to form (3) [3].
[*I Based o n work by K.
G. Kleb.
[l] H . Schweitzer and 0. Bayer, German Patent 143766 (April
19th, 1940); cf. 0. Bayer, Angew. Chem. 73, 343 (1961).
[2] J . Nelles and E. Tietze, German Patent 698 597 (Feb. 8th,1939).
[3] J . Nelles, E.Tietze, and 0. Bayer, German Patent 695331
(April 29th, 1939).
Angew. Chem. internal.
Edit.1 Val. 3 (1964) / No. 6
N-Alkylsulfonamides with sulfato groups (4) in the 8or &-position were used in order to make the dyes
originally water-soluble and then to attach them to the
p
- ~ ~ ~ I ~ - - ~ I ~ - OHO_
( ~ ~ ~ -SO,-N,\
) , - c ~
2
(2)
CH2
(1)
R
'HNRRk
(3J
-SOz-NH-(CH2)2-N:
R
textile substrate in an insoluble form produced by the
action of alkalies and heat during the dyeing; the reaction leads to sulfonylpyrrolidines ( 5 ) or sulfonylpiperidines, respectively, by intramolecular alkylation [4].
-SOZ-NH-(C~,),-OS0,~
-0
-SO,-g-C
..- C H ~ - % C H ~ - C H ~ - O S O ~
€12-CH2-OSOF
I
-4 l k y l
iiJ
j12)
(61 (11)
Their action can be explained by a neighboring-group
effect [13]. Both groups contain a strongly nucleophilic
nitrogen atom. The nitrogen atom participates in the
reaction by means of an initial nucleophilic attack on
the a-carbon atom, with displacement of the sulfato
group, to form the reactive, cyclic intermediates (8) or
(9). In the second step, these react with external nucleophilic partners to give the stable products (10) and ( I I ) ,
respectively.
+
+ z OH^
141
,CH2-CH,
+
I
-SO,N,
I
+ H 2 0 + SOFO
CIf2-CH,
t
sop
(51
Recently several research groups studied the applicability of sulfatoalkyl groups to dyes which could react
with cellulose by alkylation. As a result it was found
that the reactivity of the sulfatoalkyl groups was enhanced by the introduction of the hetero-atoms 0, s, or
N in the y- or even better in the $-position to the
sulfato group. By themselves, alkyl hydrogen sulfates
can be used as alkylating agents only under drastic
conditions.
The effectiveness of the hetero-atoms and of their
derivatives varies widely. Aryloxy groups [5] have only
a weak action, but with hydroxyl [6], alkylthio [7], and
dialkylamino groups [7,8], and with sulfonamide anions
[9] as "activators", it is possible to raise the reactivity of
the sulfatoalkyl group to the level required for practical
application as a reactive group in textile dyeing. Carboxamide groups in the P-position are not suitable as
"activators", since they react to form oxazoline derivatives by intramolecular alkylation [lo].
a) Reaction Mechanism
*
CH,
/%I
CH,
CH2-OSOQ
p
1
191
(11)
The reaction sequence indicated may be considered as
certain for compounds of type (7) by analogy with
numerous other mechanisms [14].
A proof for the mode of reaction of (6) by direct
detection of the N,N-ethylenesulfonamide (8) has not
yet been achieved. Confirmation was therefore sought
in other ways:
M) The reaction (12) + (13) is slowed down by electronattracting substituents R and accelerated by electrondonating substituents. Thus, the reaction rate (Fig. I )
Sulfonamide anions (6) or aliphatically bonded tertiary
amino groups (7) serve to activate the sulfatoalkyl
groups in the Levafix dyes.
~~~
~-
141 F. Nadler, E. Tietre, and 0.Buyer, German Patent Application
J-65961, (Nov. lSth, 1939); French Patent 976047 (March 26th,
1942).
[5] J. D . Guthrie, U.S.-Patent 2741532 (Apr. 30th, 1952).
[6] Belgian Patent 596945 (Nov. loth, 1960, German Priority
Nov. 14th, 1959), BASF; Belgian Patent 585006 (Nov. 25th,
1959, Germany Priority Dec. 9th, 1958), BASF.
[7] Belgian Patent 573466 (Dec. Ist, 1958, German Priority Jan.
28th, 1958), Bayer.
[8] German Patent 1108 176 (May 7th, 1957), BASF; German
Patent 1061 009 (March 15th, 1957), BASF.
[9] Belgian Patent 560033 (Aug. 13th, 1957), Swiss Priority Aug.
14th, 1956), CIBA; German Patent 1091259 (Dec. 14th, 1957,
British Priority Dec. 14th, 1956), ICI; Belgian Patent 565997
(March 24th, 1958, Swiss. Priority March 25th, 1957), CIBA;
Belgian Patent 569439 (July 15th, 1958, German Priority July
15th, 1957), Bayer.
[lo] P . Rehlhnder, Ber. dtsch. chem. Ges. 27, 2157 (1894).
Angew. Chem. internat. Edit. [ Vol. 3 (1964) [ No. 6
i13)
varies in the same direction and to about the same
extent as the pK-value (Table 1 ) for the dissociation of
the sulfonamido group [lS].
Since the kinetic measurements were undertaken in
0.1 N NaOH, in which the sulfonamido group is fully
[ I l l K. G . Kleb, Belgian Patent 569439 (July 15th. 1958).
(121 K . Wedemeyer, D . Dews, and W. Kruckenberg, Belgian Patent
573466 (Dec. lst, 1958).
[I31 S. Winstein and E. Grunwald, J. Amer. chem. SOC.70, 828
(1948); cf. W. Lwowsky, Angew. Chem. 70, 483 (1958).
[I41 J. Hine: PhysicalOrganicChemistry. McGraw-Hill, New York
1956, pp. 123-124.
[IS] Investigations by E. Grigat.
409
H,O
100% r
magnetic resonance and infrared spectra possesses the
constitution of N-(methoxyprop-2-yl)-p-chlorobenzenesulfonamide (19) [16].
In agreement with the data-of Winstein and Grunwald
[I71 concerning the influence of a $-methyl group upon
reactions activated by neighboring groups, (17) reacts
about 20 times faster (half-life: 18.5 min) than (14). On
the other hand, the reaction of (16) (half-life: 138 min)
proceeds more slowly than expected [17a], probably
because of steric effects caused by the sulfonamide anion.
I
i 16)
rn
10
20
30
40
Fig. 1 . Rate of the hydrolysis (12) -, (13) in 0.1 N NaOH at 50°C
in relation to the substituent R .
Ordinate: conversion I %I
Abscissa: time [hours]
07)
dissociated, the results can only be satisfactorily explained by the hypothesis of a neighboring-group effect.
If the basicity and nucleophilicity of the sulfonamide
nitrogen atom are assumed to be comparable, then the
reactivity of the group (12) must be higher, the more
basic the nitrogen atom of the sulfonamide group is or,
in other words, the greater its pK value is. Thus, although electron-release by the substituent R inhibits
dissociation of the sulfonamido group, it assists the
hydrolysis - complete dissociation being assumed - by
raising the electron density at the nitrogen atom.
0SOz-%H-C
C1
7H3
H-C H2-OC H,
(191, ni. p. (i8-69OC
These findings lead to the conclusion that a common
intermediate (18) is formed in the first, rate-determining step of the reaction of both the isomeric N-@sulfatopropy1)sulfonamides (16) and (17). After attack
by an external nucleophilic reagent upon the carbon
atom of the CH2 group which is the more positive of the
two ring-carbon atoms owing to the influence of the
methyl group, the faster subsequent reaction leads to
the end-product (19).
Table 1. pK-Values for the dissociation
KOS02-~H-(CH2)2-OSOF
NO2
H
CH3
OCH,
*
9.85
10 55
11.0
11.0s
b) Reactions during the Dyeing Process
Sulfatoalkyl groups activated by neighboring groups
can react with several nucleophiles during the dyeing
process. The preferred reaction occurs with the hydroxyl
groups of cellulose (or their anions); as a result, the psubstituted ethyl ethers of cellulose (20) and (21) are
formed.
R-SO2-NH-CH~-CH2-O-Cellulose
1201
R-CH2-N-CH2-CH2-O-Cellulose
I
Alkyl
(21)
The accompanying alkylation reactions of the reactive
groups with each other can lead to the formation of the
products (22) and (23) from compounds of type (6).
so,H2-C H2-N
R--SO,-NH-C
(22)
If this reaction proceeds according to a normal SN2
mechanism, then under equivalent conditions, the formation of two isomeric N-methoxypropylamides would
be expected from the two isomeric N-sulfatopropyl-4chlorobenzenesulfonamides (16) and ( 1 7), with constitutions corresponding to those of the starting materials. In fact, however, (16) and (17) react to give a
single N-methoxypropylamide, which from its nuclear
410
'cH,-cH~-
'..
[16] Measurement and discussion of the spectra by H . Walz.
[17] S. Winstein and E. Grunwald, J. Amer. chem. SOC.70, 830
(1948).
[17a] S. Winstein and E. Grunwald, J. Amer. chem. SOC. 70,
832-833 (1948).
Angew. C h e m . internat. Edit.
Vol. 3 (1964)
/
No. 6
Quaternary ammonium compounds (24) may be formed
from compounds of type f 7).
0-
I;JH
I
y
2
S02-NH-CH,-CH2-OS0,H
FHZ
OS03H
These reactions are desired, when they cause dyestuff
molecules to become indirectly bound firmly to the
fiber, i. e . by interspersion of other dyestuff molecules
as bridges.
The alcohols (25) and (26) may appear as a result of
hydrolysis owing to the presence of water and hydroxide
ions during the dyeing process.
R-SO2-NH-CH2-CH2-OH
(25)
R-CH2-N-CHz-CH2-OH
I
Alkyl
(26)
c) Constitution of the Dyes
(27j
02s
a:lI-3cH3
::
I
NH
OSOSH
S02-NH-CH,-C
d) Synthesis of the Dyes
The reactive group (6) is prepared from 2-aminoethanol (ethanolamine) by reaction of the amino group
with a sulfonyl chloride and by esterification of the
hydroxyl group with sulfuric acid, in whichever sequence is desired. The sulfonyl chlorides of dyestuff
intermediates or of ready-made dye-substances can be
used as starting material. In the first case, intermediates
with reactive groups are obtained, e . g . (27) and f28),
which can then be transformed into dyes, e .g. by coupling.
No. 6
H2-OS03H
In the second case, the finished dye is prepared directly
by reaction with 2-aminoethyl hydrogen sulfate.
CuPC
=
*
CuPC-(SO2-NH-CH2-CH~-0SO3H)r
copper phthalocyanine
In the case of a dyestuff which must be prepared under
conditions which decompose the reactive group, it is advisable to prepare the dyestuff with -SO~-NH-CHZ-CH~-OH
groups (29) first and then to convert this into the reactive
group by sulfatation, e . g . with concentrated sulfuric acid or
pyridine/SO,.
SO,-NH-C
Hz-C H ,-OH
so :
4
The substantivity of most dyes is reduced by replacing nuclearly bound sulfonic acid groups with reactive groups of type
(6) or with sulfonamide links. This is especially true when
all the sulfonic acid groups of this type have been replaced.
This effect is applied to make dyes with very low substantivity.
Starting from chromogens with low affinity for the fiber, only
reactive groups are used as solubility-conferring constituents
of the dyes, with the exclusion of additional ionizing groups,
such as nuclearly bound sulfo or carboxyl groups. In the
Levafix dyes, the reactive sulfatoalkyl groups must therefore
fulfil the additional function of conferring solubility in water.
In general, the solubility required for application is attained
with two reactive groups per dyestuff molecule; more than
two groups are necessary for large dyestuff molecules or for
those which associate readily.
Angew. Chem. internnt. Edii. / Vol. 3 (I964)
Q
7H2
+ HZN-CH,-CH,-OSO,H
The Levafix dyes are combinations of a chromophoric
molecule with two or more reactive groups of formulae
(6) and f 7). Representatives of the azo, anthraquinone,
vat, or phthalocyanine series, for example, serve as the
fundamental dyeing substances. Reactive groups of type
(6) are bound to the dye-substance either directly
through the sulfonamido group or by a bridge, e.g. a
benzene ring. Reactive groups of type f 7) are preferably
combined with large dyestuff molecules, such as those
found among the vat dyes, which have hydrophilic
groups (e.g. sulfonamido groups) attached to improve
their solubility.
+ HCI
HO
I
7H2
0
HN
H3CX L O ~ - N H - C ~ ~ - C H ~ - O H
(29)
Dyestuffs with the reactive group (7) are prepared
according to similar methods, starting from amino
alcohols with functional groupswhich allow combination
with the chromogens. Here the number of variations
is greater, since the bridging group to the dyestuff can
be altered at will, and since the alkyl group attached
to the activating nitrogen atom can differ. The systems
f7a) and (7b) have probved to be useful.
,C H,-c
- 9 3
-CH2-N,
c H,-c ~~-osoQ
H~-OSO~
-C H2-R,
c H ,-c H,-OSO~
41 1
e) Application
[*I, the Levafix
dyes are suitable only for dyeing processes in which
substantivity is unnecessary or even undesirable. They
are therefore used in calico printing and in pad dyeing
of native or regenerated cellulose, where they are
applied from concentrated solutions or printing pastes
containing alkali (e.g. soda, potash, or caustic soda)
and an auxiliary (e.g. urea). The yields-of fixed dyestuff
are very high (90 % or more) when the dyeing is carried
out at 100-120 "C in steam boilers or at 130-150 "C by
dry-heat treatment, provided several reactive groups and
no additional groups conferring solubility in water are
present in the dyestuff molecule. Heavy contamination
does not occur in the baths used to elute the alkali,
auxiliaries, and unreacted dye from the fiber in the
washing process which follows that of dyeing. Since it
possesses no or only low substantivity, unreacted dye
does not run onto unprinted portions of the fabric or
onto portions colored by other dyes.
As a result of their low substantivity
erto, it is almost exclusively chlorotriazines and chlorodiazines that have been described; these are the reactive
groups that are closest to cyanuryl chloride (Table 2).
The most mobile chlorine atom of these compounds is
caused to react with the amino group of a dyestuff
molecule; the remaining halogen atoms are available
for reaction with the fiber [18-201.
Table 2. Heterocyclic nitrogen compounds with mobile chlorine atoms
used as reactive groups in reactive dyes.
Reactive group
1 Trade name of the dye
Procione (ICI)
N+N
R-HNyNyC1
Cibacrone (Ciba)
Procion-H@(ICI)
c1
T h e Levafix dyes c a n b e combined not only with o n e another,
b u t also with dyes o f other classes, e.g. Naphthol-AS combinations, vat dyes, sulfuric esters o f leuco v a t dyes, pigment
dyes, a n d aniline black. Emphasis is laid upon t h e g o o d
wash-fastness of t h e colors on printed or dyed fabrics, which
is d u e to t h e stable dye-fiber bonds.
c1
!
2. Reactive Dyes with 2,3-Dichloroquinoxaline as
Reactive Group [**I
Levafix dyes with an aliphatic reactive group are little
suited for application from dilute dye liquors, or for the
cold pad-batch process which is continually gaining in
importance [18]. In order to be useful for dyeing, a
reactive dye must not display too great substantivity
but must have a reactivity towards cellulose which is as
high as possible; in addition, the reactive group should
be able to align itself sterically on the surface of the
cellulose in such a way as to favor nucleophilic substitution by a hydroxyl group of the cellulose.
These requirements are fulfilled by quasi-aromatic heterocyclic nitrogen compounds with mobile chlorine atoms
of the kind existing in cyanuryl chloride or tetrachloropyrimidine. As a result of the formation of hydrogen
bonds between the hydroxyl groups of the cellulose and
the heterocyclic nitrogen atoms, which have a high
electron density, the chlorine atoms become aligned on
the cellulose surface in a sterically favorable way.
Moreover they possess very good reactivity at the
optimum dyeing temperatures.
In the search for new reactive dyes, the greatest outcome
was therefore promised by examination of heterocyclic
nitrogen compounds with mobile chlorine atoms. Hith[*]The percentage of the total dyestuff which is attached to
the cellulose in equilibrium at pH 7 is used as a measure of
substantivity.
[**I Based on work by E . Siege1 and K . Sasse.
[18] H . Zollinger, Angew. Chem. 73, 125 (1961).
412
I
c1
Reacton@(Geigy)
Drimarene (Sandoz)
c1
c1
clQ
c1
\
c1
c1
1191 J. Wegmann, Textil-Praxis 1960, 829.
[20] H . Ackermann and P. Dussy, Melliand Textilber. 42, 1167
(1961).
[21] German Published Patent Application 1041461 (Nov. 29th,
1954), ICI; German Published Patent Application 1062 367
(Nov. 29th, 1954), ICI.
1221 German Published Patent Application I076242 (Jan. 27th,
1956), CIBA; Belgian Patent 559944 (Aug. loth, 1956), CIBA.
1231 Belgian Patent 592 148 (June 23rd, 1959), CIBA.
[24] German Published Patent Application 1067404 (Oct. 12th,
1957), BASF.
[25] Belgian Patent 607999 (Sept. 8th, 1960), Sandoz.
[26] German Published Patent Application 1088460 (Sept. 4th,
1956), ICI; French Patent 1194043 (April 5th, 1957), BASF;
Belgian Patent 572994 (Nov. 21st, 1957), Sandoz; Belgian Patent
572973 (Nov. 22nd, 1957), Bayer.
[27] German Published Patent Application 1109807 (May 23rd,
1958). Geigy.
[28] Belgian Patent 573300 (Nov. 29th, 1957), Sandoz; Belgian
Patent 578 742 (May 28th, 1958), Sandoz.
[29] Belgian Patent 604068 (May 23rd, 1960), CIBA.
Angew. Chem. internat. Edit. I Vol. 3 (1964) No. 6
a) Synthesis of New Reactive Groups
We studied heterocyclic nitrogen compounds possessing
fused-rings and mobile chlorine atoms. Hitherto these
substances had scarcely been examined. Since it was to
be expected that polynuclear fused systems would lead
to sparingly soluble dyestuffs of low molecular color
strength, we first studied 2,3-dichloroquinoxaline,
which
had previously been investigated bySasse and Weglcr[SO].
This substance is not suitable on its own as a reactive
group, since difficulties are encountered in its selective
attachment to a molecule of an amino dyestuff with
preservation of one of the mobile chlorine atoms, and
since the remaining chlorine atom is too strongly
deactivated after introduction of the substituted amino
group into the molecule.
We then looked for further useful reactive components
in other fused bicyclic systems such as 1,4-dichlorophthalazine, 2,4-dichloroquinazoline, 2-chlorobenzoxazole, 2-chlorobenzothiazo1e, and 2-chlorobenzimidazole as well as in the 2,3-dichloroquinoxaline series.
a) Quinoxaline Derivatives
Among the chloroquinoxaline derivatives (32) lo (37), 6chlorocarbonyl-2(3)-monochloroquinoxaline(34) affords the
best reactive dyestuffs; 6-chlorosulfonyl-2,3-dichloroquinoxaline (32) is not quite so well suited for the construction
of reactive dyes as the carbonyl chlorides (30) and (34),
since the substantivity of azo dyes with a sulfonamido group
in the molecule is lower than that of azo dyes with a carboxamido group.
On the other hand, we obtained valuable reactive dyestuffs (31) when we linked 2,3-dichloroquinoxaline to
amino dyestuffs by way of a chlorocarbonyl or chlorosulfonyl group bound to the benzene ring. Since the
reactivity of the chlorine atom in the chlorocarbonyl
or chlorosulfonyl group is greater than that of the
chlorine atoms in the heterocyclic nucleus, selective
acylation of primary or secondary amino groups is
achieved with preservation of the chlorine atoms in
positions 2 and 3.
f33l
m.p. 113-114°C
(3.7)
(341
m.p. 113-115°C
b. p. 138-139°C/0.28 nini
111.p.
1 2 2 - 1 23 "C
The connection of 2,3-dichloroquinoxaline to the dyestuff
through a carboxamido or sulfonamido group has an activating influence on the chlorine atoms in the quinoxaline nucleus. Model experiments showed that this influence of
substituents in the 6-position is very marked and that the
activating effect increases with increasing electron-attracting
character o f the substituent (i. e. increasingly positive value of
6-Chlorocarbonyl-2,3-dichloroquinoxaline
(30) is readily accessible technically in the way indicated in
Scheme 1 .
COOH
1321
rn. p. 8 6 - 8 7 ' C
COOH
COOH
w.
NH
c1
c1
,
c1
NHZ
m.p. 181-182°C
100°C
Oxslic acid
Hooca:xoH
PC15/POC13p
OH
Scheme 1. Synthesis of 6-chlorocarbonyl-2,3-dichloroquinoxaline.
Compound (30) can be distilled in YUCUO [31]. It is colorless
and has the typical odor of carbonyl chlorides. The substance
is only slowly hydrolysed by water, but reacts smoothly
at 40 -70 "C with aminoazo or aminoanthraquinone dyes as
well as with phthalocyanine dyes or dyestuff precursors
containing amino groups in aqueous solution, by acylation
of the amino groups with the chlorocarbonyl group.
.__
[30] K . Sasse, R. Wegler, G. Wnterstenhofer, and F. Grewe, Angew. Chem. 72, 973 (1960).
[3I] French Patent I193734 (Jan. l l t h , 1957), Geigy.
Angew. Cheni.
m.p. 284°C
infernat. Edit. 1 Vol. 3 (1964) 1 No. 6
(30). m. p. 116OC
b. p. 144"C/0.'35 m m
its Hamniett o-constant). The influence of substituents in the
aniline nucleus of 2,3-dichloroquinoxaline-6-carboxanilide
(38) is less strong, but clearly present, and is opposed to the
course of the Hanimett constants in an unusual way. The
anilide (38) can be considered as a model for dyestuffs based
on 2,3-dichloroquinoxaline-6-carboxylicacid. It is known
from studies of the dichlorotriazine dyes that dyestuffs with
the same reactive group often differ in reactivity by a factor of
10 or more (Table 3 ) [32,33].
- ~- .~
[32] H . H . Sumner and T. Vickerstaf, Melliand Textilber. 42,
1161 (1961).
[33] C. Preston and A . S. Fern, Chimia IS, 177 (1961).
413
Table 3. Pseudo-monomolecular reaction rate constants for hydrolysis
of the first chlorine atom of 2,3-dichloroquinoxaline derivatives, at
22 "C and pH 13 in aqueous dioxan. Measurements were made with
solutions of the heterocyclic chloro compounds (10-3 mole). and sodium
hydroxide (2x 10-2 mole) in 100 ml of dioxanlwater (60:40). The
chloride ion released was titrated according to the method of Volhard.
"ax1
c1
11.4
152
52
CH30CeH&O-HNHCH3-
GH5NH-OC02N-
285
1
390
460
Phthalazine a n d Quinazoline Derivatives
Introduction of a chlorocarbonyl group into the 6-position
of 1,4-dichlorophthalazine also transforms this substance,
which otherwise reacts slower (koH- = 0.012 min-1) than
2,3-dichloroquinoxaline (koH- = 0.052 min-I), into a useful
reactive component (39) [34]. On the other hand, a chlorocarbonyl or carboxamido group in the 7-position (40)
activates the chlorine atomsz'of 2,4- dichloroquinazoline,
which is already very reactive as such (koH- > 1 min-I),
so strongly that selective acylation of a dyestuff containing
an amino group by the chlorocarbonyl group is hardly
possible, and the reactive dyes formed are rapidly hydrolysed.
c1
dl
(39)
111.
Many of the azo, anthraquinone, and phthalocyanine
dyestuffs, and their intermediates frequently used in
reactive dyes and having a primary o r secondary amino
group in the molecule can be acylated with 6-chlorocarbonyl-2,3-dichloroquinoxaline. For example, the red
reactive dye (45) is obtained by stirring a suspension of
390
2600
> 300000
C1-
R
p)
b) Synthesis of the 2,3-Dichloroquinoxaline Dyes
p. 124-126°C:
mi. p. 65-68OC
b.p.
150-153"C/0.13 nini
finely powdered 6-chlorocarbonyl-2,3-dichloroquinoxaline into a n aqueous solution of an equimolar quantity of the disodiuni salt of I-amino-8-hydroxynaphthalene-3,6-disulfonic acid a t 40°C and pH 4-6,
and finally coupling the acylation product with diazotized I-aminobenzene-2-sulfonicacid at p H 7-8.
Since the relatively large 2,3-dichloroquinoxaline nucleus
markedly diminishes the solubility of the dyestuffs in water,
sometimes more groups which confer solubility in water must
be present than are required in the corresponding dichlorotriazine dyes.
Monoazo dyestuffs, such as are obtained by coupling
diazotized anilinesulfonic acids with l-phenylpyrazolones, are the basis of brilliant greenish-yellow shades;
clear orange and red shades are produced by the dyes,
e.g. (45), obtained by coupling diazotized anilinesulfonic acids with hydroxynaphthalenesulfonic acids, especially aminohydroxynaphthalenesulfonic acids. Derivatives of l-amino-4-phenylaminoanthraquinone-2sulfonic acid which contain amino groups are the basis
of brilliant blues. Dyes with a turquoise tint contain
copper o r nickel phthalocyaninesulfonic acids as chromogens. Copper, chromium, and cobalt complexes of
mono- and bisazo dyestuffs afford violet, navy-blue,
brown, grey, and black shades. The 2,3-dichloroquinoxaline dyes are known in the trade by the name
L e f a f i x - E a dyes 1341.
c) Coloring Properties of the
2,3-Dichloroquinoxaline Dyes
y) B e n z o x a z o l e a n d B e n z o t h i a z o l e D e r i v a t i v e s
We also obtained very useful reactive dyes from the 2chlorobenzoxazole and 2- chlorobenzothiazole derivatives
(41) to (44) [34]. The 2-chlorobenzoxazole dyes are very
reactive, but the colorings obtained from them are not so
resistant to boiling as those obtained from the 2,3-dichloroquinoxa1ine:dyes.
(43)
60Cl
m.p. lll-112°C
(441
An ideal reactive dye should react with cellulose as
quickly and as fully as possible and moreover be stable
t o hydrolysis in alkaline aqueous media. These requirements are not readily compatible with one another,
yet the 2,3-dichIoroquinoxaline dyes fulfil them surprisingly well.
The dyeing properties of the new reactive dyes may be
illustrated by the example of the dye (45). We have
/45), K =
146). R =
(471, R =
m.p. 134-13F"C
[34] E. Siege/ and K. Sasse, Belgian Patent 613586 (Febr. 7th,
19611, 614375 (Febr. 24<h, 1961), 614896 (March 9th, 1961),
Bayer.
414
Angew. Cliatrc. intrriiut. Edit. 1 V d . 3 (1964)
No. 6
chosen for comparison the dichlorotriazine dye (46) and
the monochlorotriazine dye (47).
The optimum temperature for dyeing from dilute liquors
is a measure of the reactivity of the reactive groups: for
(46), this is 25 “C; for (45), 40 ‘C; and for (47), 80 “C.
The 2,3-dichloroquinoxaline dyes therefore come next
to the very reactive dichlorotriazine dyes. This is also
shown by their behavior in the cold pad-batch process
[35]:
(46) 10 minutes after the addition of alkali. The degrees of
fixation obtained in the case of immediate padding correspond to the maximum yields in Figure 2. The greater the
slope of the curve in Figure 3 , the more rapidly the dye is
hydrolysed.
Figure 2 presents the proportion of dye which reacts a t room
temperature with the cellulose fabric as a function of time.
Mercerized poplin was steeped in a solution containing 10-2
mole/l of pure dye in each:case,
together ‘with the acidbinding agent and additives specified; the excess moisture
was squeezed out between rubber rollers, and the cloth was
rolled up and left standing at room temperature for different
periods of time for the dye to react with the cellulose. Finally,
the unfixed portion of the dye was washed out and estimated
colorimetrically.
2
6
Fig. 3. Stability to hydrolysis of the dyes (45) to (471 in alkaline
aqueous solution. For details see text.
Ordinate: amount of dye fixed [ % of the total quantity]
Abscissa: time after addition of alkali [hours]
10
1 2
rn
1,
8
24
Fig, 2. Dye fixed to mercerized poplin as a function of time. The figures
beside the curves indicate the identity of the dyes.
In the case of (45) and (46), 20 g/1 of soda and 100 g/1 of urea were
added; in the case of (47), 30 ml/l of 32% caustic soda and lOg/l
ofsodium sulfate were used instead.
Ordinate: amount of dye fixed [ % of the total quantity]
Abscissa: time [hours]
The reaction rate is greatest for the dichlorotriazine dye
(46) : it reached its maximum degree of fixation of 87 %
after only 15-20 minutes, while the 2,3-dichloroquinoxaline dye (45) reached its maximum (88 %) only
after 6-8 hours. On the other hand, the monochlorotriazine dye ( 4 7 ) had not reacted fully even after 24
hours, and its degree of fixation at that time lies considerably below the values for (45) and (46).
Although the 2,3-dichloroquinoxaline dye (45) reacts
with cellulose rapidly and in very high yield, its rate of
hydrolysis in the alkaline dye solution (“padding liquor”)
is considerably smaller than that of the monochlorotriazine dye and very much smaller than that of the
dichlorotriazine dye (Fig. 3) [35]. This stability to
hydrolysis in the alkaline padding liquor is important
for the cold pad-batch process, since the intensity of
the color must not drop markedly during the padding.
The dye solutions used in the cold pad-batch process were
allowed to stand a t room temperature for 0, 2, or 6 hours
after the addilion of alkali and then padded onto the mercerized poplin, which was then laid aside for 24 hours.
Moreover, a n intermediate value was measured for the dye
High reactivity towards cellulose with the greatest
possible stability to hydrolysis is desired not only in
dyeing, but also in calico printing; there has lately been
a great demand for reactive dyes with good stability
towards the alkaline printing paste and the ability to fix
out in very short steaming times of 30-60 seconds.
Although the very reactive dichlorotriazine dyes fulfil
the second requirement, they are not sufficiently stable
in the alkaline printing paste [32]. At the present time,
the dichloroquinoxaline dyes are the only ones which
have the ability to react completely within a steaming
time of 30 seconds and to keep for over three weeks in
the alkaline printing paste. Although the 2,3-dichloroquinoxaline dyes do not quite reach the standard of
wet-fastness shown by the “Indanthrene”@fast reactive
dyes based on sulfatoethyl groups activated by neighboring groups (see above), they are comparable in their
degree of fastness to the dichlorotriazine dyes.
d) Studies of the Dyeing Mechanism
The measurements of Hildebrund [36] provided information about the reactivities of the 2,3-dichloroquinoxaline dye (45) and the dichlorotriazine dye (46)
towards water and towards sorbitol (as a model for
cellulose [33]). He determined the rate constants for the
pseudo-monomolecular reaction by working up the
reaction mixtures after different times; the analysis
procedure involved paper chromatographic separation,
elution, and colorimetric estimation of the products.
As Table 4 shows, the ratio ksorbitol/kHzOis less
favorable for the dichloroquinoxaline dye (45) than for
the dichlorotriazine dye (46). The fact that (45) nevertheless attained just as high a degree of fixation as (46)
(Fig. 2) is connected with the rate of diffusion during
the heterogeneous reaction with cellulose : the dichloro-
-.
--
1361 W. Beckmann, D . Hildebrand, and H . Pesenecker, Melliand
[35] Measurements by W. Beckmann and K . Greiner.
Textilber. 43, 1304 (1962).
Ange\v. Chem. inrernat.
Edit.
1 V d . 3 (1964) 1 No. 6
415
Table 4. Rate constants for the pseudo-nionomolecular reactions of the
dyes 145) and (46) with water and with sorbitol (SO g of sorbitol/l)
a t pH 10 and 25 “C.
1
i
I
(45)
(46)
0.42
12.40
I
1 . 8 ~10-4
3 3 x 10-4
triazine dye is partly hydrolysed within the time necessary for its diffusion into the fiber [half-life period of
diffusion: 12 mi,; of hydrolysis: 30 min for (46), 550
min for (4S)J Moreover, the 2,3-dichloroquinoxaline
dye has greater substantivity than the dichlorotriazine
dye, which is attributed to the greater expansiveness and
substantivity of the dichloroquinoxaline system [37].
The elemental analysis of cotton fabric dyed by different
methods with 2,3-dichloroquinoxaline red (45) showed
that only one of the two chlorine atoms reacts with the
cellulose during the cold pad-batch process at 25 “C and
in the case of exhaustion dyeing at 40 “C. Under more
energetic conditions of fixing, e.g. with steam at 103 “C
or on baking at 140°C (“thermofixing”), the second
chlorine atom also enters into reaction with the cellulose
or water, so that thereafter only about 15 % of the
chlorine content corresponding to the second chlorine
atom is still detectable.
The studies described and the preparative work leading to
the Levafix dyes were carried out in the ZW-Laboratorium
der Farbenfabriken Bayer under the direction of Dr. D.
Delfs. Those notably concerned with the development of’
the Levafix-E dyes were Drs. R. Putter, .
I
Singer,
.
W. WOK
H. Jager, and K . Gerlach of the Wissenschaftliehes
Hauptlaboratorium der Farbenfabriken Bayer as well as
Drs. K. Greiner, H. Cutjar, and M. Soll of the Anwendungstechnische Abteilung der Farbenfabriken Bayer. We
thank Professor Otto Bayer for his intensive support of
this work.
Received, July 29th, 1963
[A 321/155 IE]
Publication deferred until now at the authors’ request
German version: Angew. Chem. 76, 423 (1964)
[37] Measurements by W.Beckmann.
Acrolein Polymers
BY PROF. DR. R. C. SCHLnZ [l]
ORGANISCH-CHEMISCHES INSTITUT DER UNIVERSITAT MAIN2 (GERMANY)
The unsaturated aldehyde acrolein is a suitable source for different types of high polymers.
Zf it is regarded as a 1,3-diene analogous to butadiene, then all the known modes of its
polymerization can be systematically described and further possibilities predicted. A survey
is given on this basis of the results obtained during the past decade. It is shown that
aerolein is one of’ the f e w monomers which contain two poiymerizable groups of differing
reactivities. This fact allows the formation from acrviein of new homopolymers, copolymers, and graft copolymers, a scope which is not encountered with many other monomers.
1. The Structure of the Monomer
As an a,?-unsaturated aldehyde, acrolein ( I ) cmtains
a conjugated double- bond system, and can thus be considered as a 1,3-diene. This comparison is expressed by
the numbering i n the formulae shown below. The
analogy between acrolein and butadiene and that between nethacrolein and isoprene is obvinus.
double bonds in acrolein possess unequal reactivities,
so that additional variations are pcssible.
According t o recent measurements [Z, Fa], the bond lengths
a n d angles in acrolein are as follows:
c=c
1.36 k 0.02 &
.
5: C,CZCJ
I 2 0 -c 3 0
c- c
1.46 i 0.03 A
.g CLCJO
120f 3 c=o
1.21
0.02 A
*
T h e (C-2)-(C-3) bond is said to exhibit 37 [3] o r 55 % [4]
double bond character. Owing t o the resultant restriction of
free rotation, geometrical isomerism is a possibility. W~igncr
et al. [ 5 ] found t h a t a t r o o m temperature a b o u t 95 % of the
s - f m n s isomer ( l a ) is present a t equilibrium. This form is
more stable t h a n t h e isomeric structure ( I b ) by 2.5 kcal/mole
Pal.
~
I t therefore follows that various polymers may be built
up from acrolein. In cmtrast t o butadiene, the two
_
_
~
~
~
[ I ] Communication No. 30 o n Acrolein Polymers. Presented a t
the Macromolecular Colloquium a t Mainz University, May 30th,
1963, and at the Forschungsinstitut fur Pigmente und Lacke in
Stuttgart (Germany), Jan. 21st, 1964. - Communication No. 29:
Makromolekulare Chem. 72, 198 (1964).
41 6
[2] H. Mackle and L. E. Siitton, Trans. Faraday SOC.47, 691
(1951); J. Fine et at., J. chem. Physics 23, 601 (1955); R . Wngner
et al., ibid. 26, 634 (1957); J. M . Holkrs, Spectrochim. Acta 19,
1425 (1963).
[2a] For further details and references o n monomeric acrolein,
see C. W. Smith: Acrolein. Wiley, New York 1962.
[3] C. A. Coukson, Trans. Faraday SOC.42, 106 (1946).
[4] 0. Polonsky. Mh. Chem. 88, 107 (1957).
[ 5 ] R . Wngner et al., J. chem. Physics 26, 634 (1957).
Angew. Chem. internnt. Edit. / VoI. 3 (1964) No. 6
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