RESEARCH

PART

DIREACTIVE DIFUNCTIONAL DYES

DERIVATIVES OF 1,3,5-TRIAZINE
Summary:

LITERATURE REVIEW
1. Reactive dyes
1.1 General description of reactive dyes
1.2 Reactive dyes with two reactive
groups. Advantages. Disadvantages.
2. Possibilities for synthesis of the compounds
of type 2-alkyl/aryl-1,3,5-triazine
II. EXPERIMENTAL PART
1. The purpose of the theme
2. Possibilities of grafting the propenyl group on
the s-triazine nucleous
3. Possibilities of grafting the benzyl rest on the
s-triazine nucleous
4. The synthesis of the epoxy group
5. Analysis
III. PROCEDURE

2
Literature Review

1. Reactive Dyes

1.1 General Description of Reactive Dyes

The reactive dyes were the first dyes, which form covalent bonds between the
dye ion or molecule and the nitrogen, oxygen and sulfur atom in the substrate. This way
an improvement in the dyeing resistance appears compared to the classical methods,
the breaking rate of carbon-nucleophile newly formed bonds is of about 103-105 from
their formation rate.
The idea of synthesizing dyes able to form covalent bonds with the substrate is
very old, but the few products firstly obtained had very complicated application
procedures and lead to the fiber degradation. Di- and monochlorotriazine reactive dyes
were the first reactive dyes for cellulosic fibers (Rattee and Stephen, 1954); they were
introduced commercially in 1956, respectively 1957. [1]
The molecule of a reactive dye has a characteristic structural form containing a
reactive group, a chromophore, a linking group between the two, and a solubilizing
group.

S [ C ( L) R ]
where S is the water-solubilizing group;
C is the chromophore (dye), denoted also by D;
L is the bridge link;
R is the reactive group. [2]

3
 There are three fundamental problems related to the reactive dyes that must be
taken into account for the design of a new reactive dye:

1. The reaction of the electrophilic group of the reactive dye with water
(hydrolysis) competes with the fixation reaction (formation of a covalent
bond between the dye and the textile substrate). The hydrolyzed dye
cannot react with the fiber. A high ratio of fixation to hydrolysis is therefore
an important requisite for high fixation and therefore for the practical
usefulness of a reactive dye.

N N

Cl N Cl Cel=cellulosic rest

Cel-ONa NaOH

D D

N N N N

Cel-O N Cl HO N Cl

Cel-ONa NaOH Cel-ONa NaOH

D D
D

N N N N
N N

N OH N OH
Cel-O Cel-O Cel-O N OH

Reaction scheme 1

2. The affinity of the reactive dyes has to be adjusted to the conditions of

application; must be neither too high, or uniform penetration of the fibers
and washing-off of unfixed dye may be difficult, nor too low, as this will
have an unfavorable effect on fixation.

3. The wash fastness of reactive dyes depends on the stability of the dye-
fiber shrinkage: the resistance to alkaline or acid hydrolysis of reactive
dyeing is closely connected with the degree of fixation because the bonds
4
 formed in the fixation reaction will be hydrolyzed in a lower, subsequent
reaction. Hence, for a reactive dye to be useful, the rate of hydrolysis of
dye-fiber bonds must be negligible compared to the fixation rate. The
resistance to alkaline hydrolysis is of practical importance in the resin
finishing of reactive-dyed cellulose fabrics. [2]
The classification of reactive dyes is done into two main groups according to their
reactive group, which determines also the dyeing mechanism:
 Reactive dyes containing groups with the ability of giving nucleophilic
substitution with the substrate (nucleophilic agent) with which they
interact;
 Reactive dyes having in their reactive system an olefinic double bond
strongly polarized, with the ability of giving nucleophilic additions with the
support on which they are applied;
 Reactive dyes with groups that react via several addition and elimination
steps with the nucleophilic group of the fiber;
 Reactive dyes with groups, which react by ester formation of a phosphonic
acid group. [1]
The first class of reactive dyes is formed of triazine reactive dyes, pyrimidine
reactive dyes, quinoxaline reactive dyes, other heterocyclic systems containing a labile
chlorine atom in the molecule and reactive dyes with one tensioned cycle in the
molecule. The second class is represented by vinylsulphonic dyes and epoxidic dyes.
In the following lines, the two nucleophilic substitutions and addition
mechanism will be presented.
The nucleophilic bimolecular (heteroaromatic) substitution mechanism:
 specific base catalyzed addition of the nucleophilic functional group
of the textile fiber to the electrophilic center of the reactive group (k1);
 elimination of a nucleofugic leaving group (k3).
This mechanism was confirmed kinetically by Zenghua’s group using a
bifunctional model compound containing a monochlorotriazine group and a vinylsulfone
group. [4]

5
 R R
R

S D k1 Y
Y 6Π k3 X
6Π C C 6Π C
k -1
N N X N Y
X

H k2 k -2 HY: nucleophilic

R functional group of the

textile substrate of water

Y
6Π C
N X

Reaction scheme 2 [1]

Nucleophilic addition mechanism has frequently an elimination step before the

addition step:
 the general base catalyzed elimination of a nucleofugic leaving group
(k1);
 the specific base catalyzed addition of the nucleophilic functional group
HY of the textile fiber (k2).

HY Cel-O
k1 k2
D CH 2CH 2 Y D CH 2 CH 2 D CH 2CH 2 O-C el
k -1 k -2
H2 O k3

D CH 2CH 2 OH

Reaction scheme 3 [2]

Since the elimination of the leaving group is generally a base catalyzed

reaction and it is independent of the textile substrate, it is possible to optimize the
formation reaction of the vinyl intermediate towards the diffusion of the dye. This fact
leads to the conclusion that varying the concentration and the pH, uniform reactive
dyeing can be obtained.
Groups that react via several addition and elimination steps are only two that
attained widespread industrial importance to date, namely the α-bromoacryloamido

6
group and its precursor, the α,β-dibromopropionylamido group. They are present in
Lanasol dyes, the most widely used reactive dyes for wool.

NH CO CH CH2 - HBr
NH CO CH CH2 S NH2
Br Br Br

NH S
NH CO CH CH2 NH CO CH CH2
NH S Br

S NH2

NH S

NH CO CH CH2
NH S

Reaction scheme 4 [1]

As shown in the reaction scheme from Reaction scheme 4, these groups are
difunctional, i.e. they are able to react with two nucleophilic site of the fiber. This leads
to crosslinking of wool, an effect that has been corroborated by experiment only
recently. [5]
Groups of dyes forming esters of phosphonic acid are principially of interest
because they are the only class of dyes, which were not discovered by dye
manufacturing chemists, but by chemists of a textile company, Burlington Industries. [6]
They were designed to be used on cellulose-polyester blends in the Thermosol process.
They were used in mixture with disperse dyes as Procilene dyes. Procilene dyes are not
produced anymore. [3]

O
(SO3H)n D PO3H2 Cel OH (SO3H)n D P OCel
OH

Reaction scheme 5 [2]

Reactive dyes are an important branch of the dyestuff industry, but in the
recent years the most developed branch of this industry was that of direactive dyes,
which would be presented in detail in the following chapter.
7
 1.2 Reactive Dyes with Two Reactive Groups.
Advantages. Disadvantages.

Reactive dyes are colored compounds which contain one or two groups capable
of forming covalent bonds between a carbon or phosphorus atom of the dye ion or
molecule and an oxygen, nitrogen or sulfur atom of a hydroxy, an amino or a mercapto
group, respectively of the substrate. Such covalent bonds are formed with the hydroxyl
groups of cellulosic fibers, with the amino, hydroxyl and mercapto groups of protein
fibers and with the amino groups of polyamides. [1]
Although it was assumed since the introduction of the first reactive dyes for
cellulosic fibers that a covalent bond is formed between the dye and the fiber during the
dyeing process, it was not easy to give definite and unambiguous experimental
evidence for such bonds. It was argued that hydrolysis, i.e. reaction of the reactive
groups with the OH group of water, was much more likely than the reaction with the OH
groups of cellulose. This problem was studied by Zollinger’s group at ETH in the early
1960’s. For a non-commercial type of reactive dye chemical evidence was found by
Krazer and Zollinger (1960). With dyeing of a dichlorotriazine and a vinylsulfone dye
(see the formulae in Figure 1 below), evidence was found in the same group by
microbiological degradation to products containing the dye bound to a glucose unit. [7],
[8]. Recently enzymatic degradation was used, again at the ETH, to demonstrate that a
dye containing two different reactive groups of the types presented in figure 1 below
form in part two bonds to cellulose. [9]

8
 Cl

N N SO2 CH2 CH2 OSO3H

N N Cl
vinylsulfone dyes
R

dichlorotriazine dye

Cl

N N

N N NH C6H4 m SO2CH2 CH2OSO3H

R
two different reactive groups dye
Figure 1 [1]

In their attempt to optimize the tinctorial capabilities of these compounds some

producers have managed to graft simultaneously, in the same molecule, two reactive
groups of the following types:
1) vinylsulfonic type compounds, like the below illustrated compound:

Cl

N N

HN N NH

N N
CH2 HCO2 S
HO3 S SO3 H

Figure 2 [3]

2) epoxydic type compounds, as this one:

OH

N
N SO 2C H2 CHC H2
H3 C
O

Figure 3 [2]

9
 The dyes of this class are usually obtained from amino dyes and epichlorhydrine
under acidic or basic conditions. During the dyeing process only the epoxidic form of the
dye appears.

H
D NH2 ClC H2 D NHC H2 C HC H2 C l D NHC H2
O O
OH

CO
D NHCH2CHCH2 Cl D NHCH2 HN
CH2
OH O

CO
D NHCH2CHCH2 N
CH2

Reaction scheme 6 [2]

Although for this class of reactive epoxy dyes only a few are of real interest, the
class is important because some dyes do not have solubilizing groups. In this case, the
hydrolyzed dye can be used as a disperse dye and so mixed fibers, containing artificial
fibers can be dyed as shown in Reaction scheme 7.

HO
D NHCH2CHCH2Cl D NHCH2CHCH2OH Cl
OH OH
Reaction scheme 7 [2]

The dyes in this category are from the class of commercial dyes known as
Procinyl (ICI, 1959) and have no solubilizing groups, having the properties of both
reactive and disperse dyes. [3]
As we mentioned before di- and monochlorotriazine reactive dyes were the first
reactive dyes for cellulosic fibers. The principle underlying the synthesis of these
reactive dyes is first to prepare the chromogenic fraction with at least one free primary
or secondary amino group, which can then be reacted with, for example cyanuric
chloride (2,4,6-trichloro-s-triazine) to give the dichlorotriazine dye. This cyanuric chloride
has the ability of replacing the three chlorine atoms by a nucleophilic reactant at three

10
different temperatures; the first at 0-1000C, the second at about 400C and the last at
more than 800C.
2,4,6-trichloro-1,3,5-triazine can be prepared starting from chlorocyan or urea,
according to the following reactions presented in Reaction scheme 8:

Cl
OH
0
180 C N N Cl2
KCN + Cl2 ClCN N N
Cl N Cl
OH N OH

O
NH2 0
O C 300 C HN NH
NH2 -3NH2
O NH O

Reaction scheme 8 [2]

The dichlorotriazine dyes can be synthesized by starting from a water-soluble

dye containing at least one amino free group (azo dye, antraquinonic, phatlocyaninic,
etc.) and cyanuric chloride at 0-100C and a pH of 6 to 6.5, maintained by adding a
Na2CO3 or NaOH solutions. The resulting products are water-soluble as sodium salts
and can be isolated by salifiation and filtration. The obtaining of such a product is
presented in Reaction scheme 9. [3]

Cl

N N

OH NH 2 Cl OH NH N Cl
N N
N N
N N

HO 3S SO 3H Cl N Cl HO 3S SO 3H

Reaction scheme 9 [3]

Sometimes, other methods can be used, in order to work with smaller molecules
in the substitution reactions and they consist in reacting the cyanuric chloride with an

11
aminic intermediate followed by coupling the product with a diazonium salt or by a
diazotation reaction of the product and coupling it with a coupling component. Coupling
reactions must in this case take place under pH conditions that do not lead to hydrolysis
of the other two chlorine atoms.

Cl
HO3S NH2
N N

Cl N Cl
OH

Cl
N
HO3S NH N
N
Cl
OH
N2

O3S
Cl
N
HO3S NH N
N
N Cl
N
OH
HO3S

Reaction scheme 10 [3]

Monochlorotriazine dyes can be prepared from the appropriate dichlorotriazine

dyes by reacting them with a primary, secondary aliphatic or aromatic amine (or other
nucleophilic agents) as in Reaction scheme 10. It is, however, also possible first to react
cyanuric chloride with a colorless amine (or other nucleophilic agent) and in a second
step to react the resulting dichlorotriazine derivatives with the amino group of the dye.
Dyes with N-heterocyclic reactive groups are prepared similarly. [1]
The synthesis of monochlorotriazinic reactive dyes has the advantage of using
dyes with small and relatively simple molecules, without the necessity of a certain
substaintivity of them towards the cellulosic fibers and which have bright colors as
compared as compared to those of direct dyes. The structures of these simple dyes
have also the advantage of a fast diffusivity into the fiber and that’s why the dyeing time
is relatively short. The commercial products of this type are from the series of Procion
and Cibacron dyes as the one in Figure 4:
12
 NaO 3 S
SO2 NH SO3 Na
N
HN N NH2
N
N N
Cu N N
N N
N
Cl

N
NaO 3S
SO2 NH2

Reactive Bright Greenish-blue Dye

Cibacron G Blue Dye
Reactive 7 Blue Dye
C.I. 74460

Figure 4 [3]

The first commercial dye with two reactive groups was probably Remazol Black
B, illustrated below (Figure 5):

SO 2C H2 CH2 OSO3 H
HO 3SOCH 2C H2 O2 S

H H H
N N O N

N N

HO 3S SO 3H

Remazol Black B
Figure 5 [1]

It is likely that the two reactive groups were introduced to increase the fixation
ratio on cellulosic fibers. The same dye is also recommended for wool, but marketed
under the name Hostalan Black SB. In contrast to Hoechst, which did not developed a
complete range of Remazol dyes containing two vinylsulfone groups in the 1960’s, I.C.I.
introduced Procion Supra dyes, which contain two monochlorotriazine groups. The
Procion Supra dyes were, however, subsequently integrated into the Procion range. [1]

13
 In 1959, I.C.I. applied for a patent relating to dyes containing two or more
reactive groups of different type. [10] Shortly afterwards Hoechst claimed dyes with the
combination of a monochlorotriazine and the precursor of the vinylsulfone group as the
one in Figure 6 below. [11]

R
N N NH C 6 H4 m SO2 CH 2 C H2 OSO 3 H

N N

Cl

Sumifix Supra Dye

Figure 6 [1]

That such dyes with two different reactive groups are, however, very interesting
for the dryers was realized only in 1970’s by Abeta’s group [12], who developed the
Sumifix Supra Dyes.
Reactive dyeing processes are known to be rather sensitive to changes in dyeing
conditions. Temperature, liquor ratio, addition of common salt and alkali are important
factors for reproducibility. As an example, the graph in Figure 7 shows the dependence
of the color yield (fixation yield) on dyeing temperature of Sumifix Supra dye. In
comparison to four dyes with only one reactive group, its color yield is significantly less
sensitive to temperature.

14
 [1]

Similar results can be observed with other parameters of the dyeing process. It
is, therefore, not surprising that most other dyestuff producers became very active in the
field of dyes with two different reactive groups.
Meyer and Müller [9] showed by enzymatic degradation of cellulose, dyed with a
dye containing a monochlorotriazine group and a sulfuric acid ester of a β-
hydroxyethylsulfone group, that a significant fraction of the dye is bound to cellulose
with both reactive groups. In 1988 [13] it was investigated the pH-dependence of the
dye-fiber bond stability of dyeing with such dyes. After the Sumifix dyes were launched
in 1980, the major dyestuff producers worldwide applied for more than 100 patents
related to dyes with two or more reactive groups.
Recently, many changes in textile industry have occurred over several years in
the dyeing house that have resulted in lower production costs and improved quality. The
study of differential bi-functional dyes offered a number of distinct advantages over
conventional mono- or bi-functional reactive dyes. Two reactive groups of different
reactivity result in dyes that are less sensitive to temperature and shade reproducibility
improved. Moreover they show minimal sensitivity to inorganic salts and to alkali and
are less affected by changes in liquor ratio.

15
 The presence of two types of bonding to the fiber would result in certain
consequences for fastness properties. Color shade of difference bi-functional dyestuffs
is bright, comparing with vinylsulfone type dyes. It takes short to wash color, because it
has good wash-off property in washing process. The affinity and diffusion behavior and
the amount of unfixed dyestuff are the main factors affecting the cost of the washing-off
processes. Optimum wet fastness can only be obtained if all unfixed dyestuffs are
removed from the fibers. [16]

The most important advantages of these dyes are as follows:

 Chemical bonding between vinylsulfone group and cellulosic fiber is very

stable to acid hydrolysis so that the stability of the dye goods with the lapse of
time is superior.
 The substaintivity of reactive dyes which has been hydrolyzed without
reacting with fibers, i.e. unfixed dyes, is very low, so that after dyeing the
wash off properties of the dye is good.
 By using triazine as a bridge link, a wide range of chromophore with excellent
fastness property can be selected.
 The increase in substaintivity due to triazine ring improves the degree of
exhaustion and fixation of dyes.
 Because of two different reactive groups the range of optimum dyeing
temperature is achieved and it improves the reproductivity in combination
dyeing.
 Migration properties and levelness: reactobond difunctional dyes have better
migration, which works effectively to give good levelness because of the
different reactive groups in the same dye.
 Reactobond difunctional dyes give best result in trichromatic combination with
excellent levelness with best wash off properties in unfixed dyes.

With two reactive groups, reactobond difunctional dyes get fully exhausted and
better fired which reduces the pollution load in the effluents. Dyes are the integral part
of wet processing to make the fabric colorful but in spite of the best technological
developments cent percent of the dye exhaustion is not possible. The unused dyes
make the effluent colored. This effluent when discharged into the water bodies transfer
color to it and effects the photosynthetic activity of aquatic plants as well as organic
nature of dyes imbalances the ecosystem. The removal of color from the textile effluent

16
is necessary to protect eco-balance. Various methods have been developed to
decolorize textile waste water like membrane-filtration, reverse osmosis, flocculation
etc. but most of these are expensive. Adsorption is another suitable method for
decolorisation of effluents. An attempt has been made to work out for a natural and
cheaper alternative based on surface adsorption for discoloration of effluent using a few
natural adsorbents like charcoal, wood ash, brick powder, sugarcane bagasse and tea
leaves ash. Nowadays, the work efficiency of various natural adsorbents is compared
by using their action on effluent from a dye bath prepared for dyeing of polyester/cotton
(65:35) blend. For this two class of dyes were used, i.e. disperse dyes for polyester and
reactive difunctional dyes for cotton component. Two bath two step and one bath two
step processes are used for dyeing. The natural adsorbents tried are tea leaves ash,
wood ash, charcoal, sugarcane bagasse and brick powder as cheap alternatives to
activated carbon. [17]

The subject of reactive dyes has been reviewed extensively. There are three
monographs written by Lukós and Ornaf (1966, in Polish), by Kriechevsky (1968, in
Russian) and by Beech (1970, in English). A volume of the series of the books on dyes
edited by K. Venkataraman is devoted exclusively to reactive dyes. [14] More recently
reviews and chapters in books have been written by Ratee (1978,1984), by Hallas
(1984), by Rys and Zollinger (1989) or by Renfrew and Taylor (1990). Clonis et al.
(1987) published a book on reactive dyes in protein and enzyme technology.

The growth rate of reactive dyes for cellulosic fibers consumption is 3.9% per
annum worldwide. This is four times the growth rate of other dyes for these fibers
(Renfrew and Taylor, 1990). Particularly high is the change of production volume of
reactive dyes in Japan. From 1981 to 1989 it increased from 4390 to 14998 tones per
annum (Abeta and Imada, 1990b).

17
 2. Possibilities for synthesis of the compounds of
type 2-alkyl/aryl-1,3,5-triazine

1,3,5-Triazine is the cyanhidric acid trimer and it is an unstable product, which

by hydolysis is easily transformed to ammonium formiate. On the other hand, its
derivatives are stable compounds. Cyanuric chloride is used in the dye industry to
produce triazinic reactive dyes.
The obtaining of the triazinic reactive dyes is usually done by the condensation
of a water-soluble amino-dye with an equimolecular quantity of cyanuric chloride. The
cyanuric chloride is previously poured into acetone and easily precipitated in water with
ice. The reaction is taking place in water at 0-5 0C and pH~6. The pH value is kept
constant by adding in portions a Na2CO3 or a NaOH solution, the end of the reaction
being marked by the raising of the pH because of the complete consumption of alkali.

OH NH 2
Cl N Cl
N N
N N (Na2CO3)

NaO3 S SO 3Na - HCl

Cl

N Cl
OH NH
N N N N

Cl
NaO3S SO3Na

Reaction scheme 1 [1]

18
 Sometimes, on the cyanuric chloride is grafted an aminic intermediary and the
resulted product can couple without the risk of the remained chlorine atoms hydrolysis.
Then it is treated with a diazo component, as illustrated before in chapter 1.2, Reaction
scheme 10.
In other cases the cyanuric chloride reacts with an aromatic diamine through
one of the amino groups, and then the formed product is diazotated at low temperature
and coupled in specific conditions for the remained chlorine atoms hydrolysis not to
occur.
Cl N Cl N Cl
HO3S NH
HO 3S NH2 N N (Na2 CO 3)
N N
- HCl H2 N
H2N Cl pH=6;0-50C Cl
HNO2
0
0-5 C

O3S NH N Cl

N N
N N
Cl

CO NH OH
[Na 2 CO 3 ]
0
pH=6;5 C
HO 3S SO 3H

HO3S NH N Cl

CO NH OH
N N
N N
Cl
HO 3S SO 3H

Reaction scheme 12 [1]

In all the cases presented above, the products are soluble in water as sodium
salts and are isolated by salifiation and filtration. Since this dichlorotriazine compounds
are easily hydrolyzed under traces of acids, the colorants pastas obtained this way are
mixed with Na2HPO4 and K2HPO4 for keeping the pH approximately 6. Then they are
dried in vacuum at regular temperature.

19
 II. Experimental Part

1. The Purpose of the Theme

This work has the purpose of synthesizing a dye having both features of
reactive and disperse dyes, which can be used in dyeing natural and synthetic fibers
mixtures. The present technology for the dyeing of this mixtures of fibers is done by
successive application of the reactive dyes on cellulosic fibers and then of disperse
dyes on polyesteric fibers. Since this dyes don’t have the same chromoforic group, at
the end a post-uniformization treatment is realized. This treatment does not preserve
the brightness and hue of the initial dyes. It more likely mediate the bathochromic shift
of the two chromophores used.
To eliminate all these disadvantages a single dye having the tinctorial abilities
of the both classes of dyes will be of real interest.
So it was observed the tendency of epoxidic difunctional reactive dyes of
having both features of reactive dyes: reactive groups capable of forming covalent
bonds with the cellulosic fiber, and epoxy groups, which by hydrolysis can be fixed onto
a polyesteric support. Such a dye will have a real practical interest, since the same
chromophoric group will be used for dyeing and this way no post-uniformization
treatment will be necessary.
For realizing this purpose we started from a reactive difunctional dye with a
triazine bridge link, which has improved qualities than monofunctional dyes. The triazine
gives the possibility of selecting a wide range of chromophore with excellent fastness
properties and improves the degree of exhaustion and fixation. On the other hand, the
presence of two different reactive groups in the molecule gives a better reproductivity in
combination dyeing and better migration properties and levelness.

20
 Experimentally we have decided to obtain a dye with the following structure:

Cl

N N

D N CH 2 CH CH 2
O

direactive difunctional epoxy dye

Figure 8

For this purpose we started our synthesis from the cyanuric chloride (2,4,6-
trichloro-1,3,5-triazine), and grafted a diamino-copper phtalocyanine cromophore. In
order to keep a low molecular mass for this substance below the limit at which it won’t
have any substaintivity, we choose to graft the 3-propen-1-il rest. Since the
chromophore is not very reactive at room temperature, and the first chlorine atom in the
cyanuric chloride molecule is substituted at room temperature, the choice was to graft
first the epoxy group. But epoxy is not a very reactive group, so we needed a group with
increased reactivity, which could be afterwards oxidated to epoxy. This group was the
allyl chloride, more specifically its organo-magnesian derivative. The reaction scheme,
in this case, will look like that:
Cl
Cl

0 N N
N N 0-20 C
ClMgC H2 CH CH 2
Cl N
Cl N
Cl CH2 CH CH2
0
0-20 C
Diamino copper
ClC H2 CH CH2 Mg phtalocyanine
0
40 C
Cl Cl

N N N N

N N
NH CH 2 CH CH 2 NH CH 2 CH CH 2
N N
O
N N
N N N N
Cu RCOOOH
N Cu
N N 0
N N
0 C N

N N
H2 N H2 N

Reaction scheme 13
21
 This dye can be hydrolyzed and used as a disperse dye, as we can see from
reaction scheme 14 below:

Cl

N N Cl
H2O
N N N
NH CH2 CH CH2
N O N
NH CH2 CH CH2
N N N
N
Cu OH OH
N N N
N N
N
Cu
N N N N
H2N
N
H2N
0
aprox. 100-120 C

Polyester Fibers
Reaction scheme 14

The two hydroxyl groups make the dye soluble in water; therefore it can make a
dispersion in water and dye synthetic fibers, as polyester fibers are. These groups are
also capable of forming hydrogen-bridges, as required for disperse dyes.
In order to prove the tinctorial capacities of this dye, a qualitative study was
made by comparing our dye with two monoreactive dyes, having the same
chromophoric group, but only one of the two reactive groups.
This way, a dye with a labile chlorine atom and a benzyl radical grafted onto the
nucleous was obtained and also a dye with an epoxy group and an aniline rest
substituting the remaining chlorine atom. The two compounds were synthesized as
follows:
 The first one, having chlorine reactive group was synthesized like this:
 A nucleophilic substitution of the first chlorine atom with the organo-
magnesian derivative of benzyl chloride;
 A nucleophilic substitution of the second chlorine atom with the
chromophore, diamino-copper phtalocyanine;

22
 The second, having a 3-propen-1-yl reactive group, was synthesized as presented
below:
 A nucleophilic substitution of the first chlorine atom with the organo-
magnesian derivative of allyl chloride;
 A nucleophilic substitution of the second chlorine atom with aniline;
 Nucleophilic substitution of the third chlorine atom with the same
chromophoric group of diamino phtalocyanine;
 Oxidation of the previously obtained compound in order to obtain an
epoxy group.
These two monofunctional dyes have on the triazinic bridge one of the two
reactive groups of our newly synthesized dye. The two newly added groups, benzyl
chloride, respectively aniline, are not reactive groups does not react with the hydroxyl
groups of the cellulosic fibers. Their reactivities are comparable since they only differ by
one substituent. But also they are a proof of the improved qualities of difunctional
direactive dyes. The one reactive group within can form covalent bonds with one site of
the fiber, but for difunctional dyes the substance can react with two active sites of the
fiber. This improves the fixation properties of the dye. Besides that, our dye can also
make a dispersion in water to color the polyester fibers having the same chromophoric
group the final coloration will be uniform.
This work is a team effort. The present thesis is based experimentally only on the
synthesis of the differential difunctional reactive dye: the epoxide of 2-(3’-propen-1’-yl)-
4-(diamino copper phtalocyanine)-6-chloro-1,3,5-triazine, represented by the middle
branch in the Reaction scheme 15. The syntheses of the other two monofunctional
reactive dyes were realized by a colleague, with the possibility of comparing the results
in further tests.
The purpose of the work doesn’t consist only in the synthesis of the dye, but also
in confirming the structure of the obtained dye through IR analysis and melting points.
The comparison with the two monofunctional dyes is done in order to obtain a dye with
comparable affinity for the cellulosic, as well as for polyesteric fibers. This work is only
the beginning of a way, which might be continued by testing the obtained dye on the
fiber mixtures and eventually improve its tinctorial qualities.
For a better understanding of our purpose the three syntheses were illustrated in
parallel in the Reaction scheme 15.

23
 Cl

N N

Cl N Cl
CH2MgCl ClMgCH2 CH CH2
CH CH2
CH2MgCl
0 0
0-20 C 0-20 C 0
0-20 C
Cl Cl Cl

N N N N N N

CH2 N Cl CH2 CH CH2 N Cl CH2 CH CH2 N Cl

0 NH2
40 C

Cl
Diamino copper Diamino copper
phtalocyanine phtalocyanine N N
0 0
40 C 40 C
CH2 CH CH2 N NH2

Diamino copper
phtalocyanine
0
over 80 C

H2C CH CH2 N Cl
Cl H2C CH CH2 N NH2
N N
N N N N

CH2 N HN
HN HN
N
N N
N N
N N N N N
N N Cu N
N Cu N N Cu
N N N
N N N
N N
NH2
NH2 RCOOOH
0 RCOOOH NH2
0 C 0
0 C

H2C CH CH2 N Cl H2C CH CH2 N NH2

O O
N N N N

NH NH
N N

N N N N N
Cu N
N Cu
N N N N N

N N
H2N H2N

Reaction scheme 15

24
 2. Possibilities of grafting the propenyl group on
the s-triazine nucleous

The propenyl group is a 3-propen-1-il group coming from propene. What is

special about this substance it is its ability of keeping its double bond during some
reactions. We refer to the allylic substitution reactions, where the halogen atom is not
additioned to the double bond but it is substituted to the neighboring carbon atom.
The most reactive s-triazine derivative is the cyanuric chloride. It undergoes
nucleophilic substitution reactions to all the three carbon atoms. Since halogenated
derivatives possessing the same halogen atom give no reactions, we need a derivative
of allyl chloride able to react to the cyanuric chloride. This derivative is the Grignard
derivative of allyl chloride, which is an exception from the rule having a very reactive
chlorine atom. [17]
The reaction in this case will look like this:

Cl Cl

N N N N
CH2 CH CH2MgCl MgCl2
Cl N Cl Cl N CH2 CH CH2

Reaction scheme 16

The possibilities of grafting the propenyl group onto the triazine nucleous are
reduced because of the limited options regarding keeping the double bond intact. But
this work does not propose an extensive study over this problem, so we show this
possibility, which has been proven by experimental studies.

25
 3. Possibilities of grafting the benzyl rest on the
s-triazine nucleous

The benzyl chloride is a substance with increased reactivity. The easiest way to
graft it onto the triazine nucleous is to substitute it to cyanuric chloride. Yet it has no
ability of reacting with cyanuric chloride by itself, but its Grignard derivative has. [17] By
the reaction between the two, the compound presented in Reaction scheme 17 will be
obtained.

Cl Cl

N N N N
ClMgH2C MgCl2
Cl N Cl Cl N H2C

Reaction scheme 17

This feature of the benzyl Grignard derivative is due to the increased reactivity of
its carbon atom. Besides it and the allyl chloride only the α -halogen-ethers have the
unique ability of reacting with organo-halogenated compounds. [17]

26
 4. The synthesis of the epoxy group

The epoxy group is usually synthesized by alkenes’ oxidation with organic per
acids (A.N.Prilejaev, 1909). The most used peracids are the monoperphtalic or better
the peracetic acid. [17]

HO
C H O C O H O C C R
O
C O C C O C R C O
O R

Reaction scheme 18

This synthesis is probably catalyzed by acids and goes through the mechanism
illustrated in Reaction scheme 19 below:

R CO R CO R CO
+ C
O H + -H
+ C
H O H O O
H O C
C +
H O C
H O C

Reaction scheme 19

Peracetic acid used in this reaction is made as a solution in acetic acid. Another
method might be the usage of perbenzoic acid or tert-butyl hydroperoxide in ethylic
ether. [18]

27
 5. Analysis

The compounds obtained during the experimental part of this work were
characterized by melting points and Infrared spectra. The IR spectra are attached to the
end of this chapter.
The first compound obtained during this synthesis is 2-(3’-propen-1’-yl)-4,6-
dichloro-1,3,5-triazine, illustrated in Figure 9 below.

Cl

N N

Cl N CH2 CH CH2
Figure 9

IR characteristic bands Melting point

C=N in triazine 1600
ν CH 2 asymmetric 2990 1830C
C=C aliphatic 3050

The second compound is 2-(3’-propen-1’-yl)-4-(diamino-copper-phtalocyanine)-6-

chloro-1,3,5-triazine (Figure 10), which was also characterized by melting points and IR
spectra.
Cl

N N

NH N CH2 CH CH2
N

N N
N
Cu
N N N

N
H2N

Figure 10

IR characteristic bands Melting point

28
 γ 4H+ adjacent
CH 710
ν CH 1090
ν CN aromatic 1260
C=C aromatic 1470,1490 >3000C
C=N in triazine 1600
C=C aliphatic 3050
C-NH in cromophore 3360

The third compound is an epoxy derivative (Figure 11) of the previous obtained
compound, but because of the quality of the spectra it is hard to be read. Still, it can be
observed the missing of the 3050 IR band, indicating the converting of the double bond
to epoxy.

Cl

N N

NH N CH2 CH CH2
N O

N N
N
Cu
N N N

N
H2N

Figure 11

The melting point of this compound is also higher than 3000C.

Bibliography:
1. H. Zollinger, Color Chemistry, VCH, Weinheim, New York, Basel,
Cambridge, 2nd edition, 1991
2. St. Tomas, Organic Dyes and Pigments-Lecture Notes, UPB, DSI, 1996

29
3. L. Floru, F. Urseanu, C. Tarabasanu, R. Palea, Chimia si tehnologia
intermediarilor aromatici si a colorantilor organici, Ed. Didactica si
Pedagogica Bucuresti, 1982
4. H. Liqi, Z. Zhenghua, C. Konchang, and Z. Faxiang, 1989, Dyes and
Pigments, 10,195
5. P. Ball, U. Meyer, H. Zollinger, 1986,Text. Res. J., 56,447
6. B.L. McConnell, L.A. Graham, and R.A. Swidler, 1979, Text. Res. J.,
49,458
7. O.A. Stamm, H. Zollinger, H. Zahner, and E. Gaumann, 1961, Helv
Chim Acta, 44,1123
8. P. Hagen, E.T. Reese, and O.A. Stamm, Helv Chim Acta, 1966,
44,2278
9. U. Meyer, and S.M. Muller, 1990, Text. Chem. Col., 22(12)26
10. P.W. Barker and J.S. Hunter, 1959, I.C.I., Brit. Pat. 901434
11. H. Boedecker, G. Langbein, K. Sommer, H. Zimmerman, K. Berner,
1961, Hoechst, US Pat 3223470
12. S. Fujioka, and S. Abeta, 1982, Dyes and Pigments, 3,281
13. M. Matsui, U. Meyer, H. Zollinger, 1988, J. Soc. Dyes Colour, 104,425
14. E. Siegel, K. Schundehutte, and D. Hildebrand, 1972, In:
Venkataraman K. (ed): The Chemistry of Synthetic Dyes, Vol VI,
Academic Press, New York
15. K.H.Sung, The Management of Color through Bifunctional Reactive
Dyestuffs
16. J.K. Sharma, and M.K. Arora, Decolorisation of Textile Effluent Using
Natural Adsorbents, 2001, 127,021
17. C.D. Nenitescu, Chimie organica, Volumul1, Ed. Didactica si
Pedagogica, Bucuresti 1980, editia a-VIII-a,
18. Becker, Berger et all., Organicum- Chimie organica practica, Ed.
Stiintifica si Enciclopedica, Bucuresti, 1982.

30