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CHAPTER-1

PYRAZOLONE BASED REACTIVE &ACID DYES

Introduction and Literature Review

Present Work

Experimental

Chapter-1 Pyrazolone based Reactive and Acid Dyes

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INTRODUCTIONDyes are intensely coloured substance used for the colouration of various

substrates such as paper, leather, fur, hair, foods, drugs, cosmetics waxes, greases,

petroleum products, plastics and textile materials. They are retained in these

substrates by physical adsorption, salt or metal complex formation, solution

mechanical retention, or by the formation of covalent chemical bonds.

The colour of a dye is due to electronic transitions between various molecular

orbitals, the probability of these transitions determining the intensity of the colour.

Witt proposed that in order for an organic molecule to be classified as a dye it must

contain two types of group.

The choromophore e.g. –N=O, -NO2, -N=N-, >C=C, >C=O, -CH=N-, -

N=N→O, -N=N-NH and quinonoid groups which are applied to a completely

conjugated system, and an auxochrome e.g. –OH, -NH2, -NHR or –NR2.

It is the interaction of the auxochrome with the chromophore that develops

colour intensity. It is now recognized that not only salt-forming groups but also

groups affecting the polarity of the system act as auxochromes. e.g. –CH3, -Cl, -Br, -

OH, -OCH3, -NH2, -NR2, and –O- and electron accepting groups such as –NH3, -

SO2NH2, -CO2R, -CN, -COCH3, -CHO and –NO2. The most effective auxochromioc

groups are those which participate directly in the conjugation with the chromophore

system.

Dyes are applied to textile fibers by two distinct processes: dyeing and

printing, of which dyeing is much more extensively used.

Dyes may be classified in accordance with their chemical constitution or their

application to textile fibers and for other colouring purposes. It is by application

methods rather than by chemical constitution that dyes are differentiated from

pigments.

Nomenclature of Dyes

There is no definite nomenclature of dyes, and most of the dyes have

several different names for the same dye because generally the dye manufacturers

assign their own names to a single dye. To overcome this difficulty a colour index has

been compiled by the dyes and colourists. In this colour index each dye is given its

individual colour number (C.I.No) [1,2].


2

Classification of Dyes According to their Chemical Constitution:

Class Subclass Example

Nitro ---------- Napthol yellow s

Nitroso ---------- Fast green o

Azo Monoazo Acid orange 2

Disazo Congo red

Trisazo Direct black EW

Polyazo --------------

Mordant azo Eriochrome black T

Stillbene azo Chrysophenine G

Pyrazolone azo Tartrazine

Diphenylmethane ---------- Auramine O

Triphenylmethane ---------- Malachite green

Anthraquinonoid ---------- Alezarine

Acridine ---------- Acridine orange NO

Thiazole ---------- Basic yellow T

Azine ---------- Safrainine T

Oxazine ---------- Capri blue GN

Thiazine ---------- Methylene blue

Cyanine Methine, Quinoline Astrafloxine FF, Krptocyanine

Sulphur ---------- Sulphur black T

Lactone ---------- Resoflavine W

Aminoketone ---------- Helindon brown CR

Hydrosyketone ---------- Alazarin dark green W

Indigoid ---------- Indigo

Sulphurizedvat dyes ---------- Hydron blue R

Phthalocyanine ---------- Monastral fast blue BS


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Classification of Dyes by Application or Use Method:

Class Principal

Substrates

Method of Application Chemical type

Acid Nylon, wool, silk,

paper, inks, and

leather

Usually from neutral to

acidic dyebaths

Azo, premetallized azo,

anthraquinone,

triphenylmethane,

azine, xanthenes, nitro

and nitroso

Azoic

components and

compositions

Cotton, rayon,

cellulose acetate and

polyester

Fiber impregnated with

coupling components and

treated with a solution of

stabilized diazonium salt

Azo

Basic Paper,

polyacrylonitrile,

modified nylon,

polyester and inks

Applied from acidic

dyebaths

Cyanine, hemicyanine,

diazahemicyanine,

diphenylmethane,

triarylmethane, azo,

azine, xanthenes,

acridine, oxazine and

anthraquinone

Direct Nylon,rayon,paper,

cotton, and leather

Applied from neutral or

slightly alkaline baths

containing additional

electrolyte

Azo, phthalicyanine,

stilbene and oxazine

Disperse Polyester,

polyamide, acetate,

acrylic and plastics

Fine aqueous dispersions

often applied by high

temperature/ pressure or

lower temperature carrier

methods; dye may be

padded on colth and baked

on or thermofixed

Azo, anthraquinone,

styryl, nitro and

benzodifuranone

Fluorescent

brighteners

Sops and detergents,

all fibers, oils,

paints, and plastics

From solution, disperision

or suspension in a mass

Stilbene, pyrazoles,

coumarin and

naphthalimides


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Class Principal

Substrates

Method of Application Chemical type

Food, drug and

cosmetic

Food, drug and

cosmetic

Azo, anthraquinone,

carotenoid and

triarylmethane

Mordant Wool, leather, and

anodized aluminium,

Applied in conjuction with

Cr salt

Azo and anthraquinone

Oxidation bases Hair, fur and cotton Aeomatioc amines and

phenols oxidized on the

substrate

Aniline black and

indeterminate structure

Reactive Cotton, wool, silk

and nylon

Reactive site on dye reacts

with functional group on

fiber to bind dye covalently

under influence of heat and

pH (alkaline)

Azo, anthraquinone,

phthalocyanine,

formazan, oxazine and

basic

Solvent Plastics, gasoline,

varnishes, lacquers,

stains, inks, fats, oils

and waxes

dissolution in the substrate Azo, triphenylmethane,

anthraquione and

phthalocyanine

Sulfur Cotton and rayon Aromatic substrate vatted

with sodiym and reoxidized

to insoluble sulfur-containg

products on fiber

Indeterminate

structures

Vat Cotton, rayon and

wool

Water-insoluble dyes

solublized by reducing with

sodium hydrigensulfite,

then exhausted on fiber and

reoxidized

Anthraquinone

(including polycyclic

quinines) and indigoids

Majority of synthetic dyes used in dyeing of textile fibres are mainly azo dyes

which require huge quantity of carcinogenic aryl amines and naphthols in their

synthesis. The effluents coming out of the dyes factories are nit only harmful to the

flora and fauna but to the human being living in those areas as well to the user. The

national and international awareness about depletion of natural resources, ecological

balance, pollution problems developed due to use of hazardous chemicals have forced


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the scientists to develop safer alternate to azo dyes. The use of azo dyes has been

banned in Germany, USA, European countries as well as in Indian sub-content. As a

result of health hazard created by these synthetic azo dyes, there is again a great

demand to revive the age old art of dyeing with natural dyes because they are non-

toxic and non carcinogenic in comparison to synthetic azo dyes. Natural dyes are

good alternate to synthetic azo dyes but due to high coast involved in isolation and

separation of natural dyes, meager natural resources to cultivate dye yielding plants,

inadequate degree of fixation and fastness properties forced the scientists to

synthesized non azo dye such as anthraquinones, flavonoids and chalcones etc. The

data generated during the work may be used as basis for studying the economics and

viability of dyes on commercial scales [3-7].

REACTIVE DYESReactive dyes are coloured compounds which contain one or two groups

capable of forming a covalent bond between a carbon or phosphorous atom of the dye

ion or molecule and an oxygen, nitrogen or sulphur atom of a hydroxy, an amino or a

mercapto group respectively, of the substrate. These dyes are generally used on higher

value mercerized cloths [1,2]. Improvements in the structure of reactive dye

chromogens and in the structure, selection and number of reactive groups have led to

increased use of reactive dyes [8-10].

Reactive dyes may be called an important Landmark in the development of

synthetic dyestuffs. Their ease of application, wide shade range, high brilliancy and

excellent wet fastness properties make them preferred choice for much cellulosic fibre

dyeing application. The chemical reaction between the dye and the fiber, enable one

to get assortment of bright, attractive shades of adequate fastness, with considerable

ease of dyeing.

Reactive dyes comprise a chromophore and a reactive group and owe their

excellent wet fastness to the formation of covalent bonds with the fibre. They differ

fundamentally from colouration products that depend upon physical adsorption or

mechanical retention and in some ways can be regarded as the, ‘high-tech’ end of the

textile dyeing business. From a manufacture stand point they represent not only a

relatively high growth and high added value sector but also the one that is still


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undergoing rapid technological change. They, therefore, offer opportunities for

innovation and patent protection.

The reason for such a rapid increase in demand is primarily due to the excellent

characteristics of reactive dyes, e.g. simple dyeing operation and their brilliant shades,

excellent wet fastness which has increasingly been accepted within the industry.

However, with growth in the usage of reactive dyes, additional properties have been

demanded by dye workers and apparel manufactures [11-14] in particular high

fixation in exhaustion dyeing and high fastness to chlorine perspiration, light and

washing in presence of peroxides.

The first dye of this group was introduced in 1956 under the name ‘procion’ by

the dyestuffs division of Imperial chemical Industries Ltd. Most of the procion dyes

are water soluble, easily applied and because the reactive group may be attached to

almost any coloured molecular system, can be used to produce both very bright and

very dull shades of all colours. Procion dyes are greatly superior to direct cotton dyes,

which have high affinity because of their distinctive advantages. The procion dye and

fiber reactive dyes have made a greater impact on dyeing technology in the few years

since their introduction then any other class of dyes in so short time.

Reactive dyes are widely used for dyeing and printing protein fibres. The

hydrophilic group of conventional reactive dyes is an anionic group, eg. Sulphonate or

Carboxylate, but the hydrophilic group of reactive cationic dyes is cationic [15].

Close attention has been paid to the fact that the existence of cations results in

some of the colouristic properties of these kind of dyes [16]. Reactive dyes are well

known and applied for dyeing of different materials [17], among them triazine

derivatives have an important place.

Reactive dyes are now a major group of dyes in spite of late entry into the

family of synthetic dyes have attained a commercial status. No slackening of activity

in this field is seen from the large number of patent specifications and several ranges

which continue to appear in the market [18-20].

CONTITUTION OF REACTIVE DYES:

In principle, a reactive dye should contain a leaving group (X) which can

undergo nucleophilic displacement by hydroxyl group of cellulose in presence of

aqueous alkali (Dye- X + Cell-O- → Dye-O-Cell + X- ) or an activated –C=C- bond


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which is able to add a hydroxyl group of cellulose (-CH=CH2 ) + Cell-OH → -CH2 -

CH2-O- Cell).

Reactive dyes are the only textile colouration products designed to furnish

covalent bonds between dye and substrate during dyeing. Although many different

reactions can be used for fixation, two main types are exploited commercially, i.e.

heteroaromatic nuclephilic substitution and addition to an activated alkane [21-24].

Thus, the majority of reactive dyes can be distinguished into two categories by

their reaction modes as:

(i) Nuclephilic addition dyes:

+ Y-

CH CH2 CH CH2 Y- + H+

CH2 YCH2

(ii) Nucleophilic addition- elimination dyes:

The general formula of a reactive dye is given as,

a – c – b – R

Where ‘a’ is water- solubilizing group. Generally, -SO3Na and –COONa groups are

used as a water-solublizing group; ‘b’ is a bridging group which links together

chromophoric ‘c’ and reactive ‘R’ systems. The commonly used bridging groups are –

NH-, -N (CH3)- and CH2O- etc. The bridge unit effects to a great extent, the reactivity

of the dye and the tendency of the corresponding dyeing to hydrolyze. ‘R’ is a

reactive group. The dye- fiber compound may have the properties of an ester or ether,

the precise nature and stability of the dye fiber bond will depend on the reactive

group.

Chromophoric system ‘C’ is mainly responsible for the colour of the dye.

Various types of shade can be obtained by changing the chromophoric system. From

the large number of suggested chromophoric systems azo, anthraquinone and

phthalocyanine derivatives have achieved great economical importance. Dyestuffs of

these groups form the hard core of all commercial reactive dyestuff ranges.


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DEVELOPMENT OF REACTIVE DYES:

The first industrially important reactive dye systems were developed for wool

using chloroacetylamino [25] and the chloroethanesulfonyl groups [26]. Vinylsulfonyl

and 2-sulfo oxy ethanesulfonyl groups were found to be applicable to both wool and

cellulose. Heyna and Hoecht patented some of the first dyes of this type [27,28]

Vinylsulfone dyes continue to be of great importance. Cross and Bevan first

successfully fixed the dyes covalently on to cellulose fibers [29], but their multi

steps process was too complicated for practical application. Early attempts by

Schroeter with sulfonyl chloride based dyes was unsuccessful [32] but Gunther later

successfully fixed the derivatives of isotoic anhydride on to the cellulose fibres [ 33].

A Patent taken by Hochest [27] for wool under the trade name Ramalan

followed a year later by the Cibalan dyes from Ciba-Geigy, which contained

monochlorotriazinyl reactive groups [29]. In 1953 Rattee and Stephen were able to fix

chlorotriazine containing dyes on to cellulose in basic, aqueous solvents, representing

an economic break through for the reactive dye concept [30].

An alternative approach is to modify the fibres themselves and then introduce

the coloration e.g. cellulose can be reacted with 4-nitrobenzyldimethyl, phenyl-

ammonium hydroxide or 3-nitro benzyloxymethyl pyridinium chloride followed by

reduction, diazotization and coupling to a dye [34]. Another process involved treating

the cellulose with cyanuric chloride in an organic solvent and then reacting the

product with an amino group containing dye [30].

Previous work on the reaction of soda cellulose with cyanuric chloride [35,36]

led to a useful industrial method for the production of dyeing in which a covalent

bond was formed between the dye and the fibre [37]. This development resulted in the

introduction of the first range of reactive dyes for cellulose marketed by ICI in 1956

as the Procion M dyes. The initial members of this range were all highly reactive

dichlorotriazinyl derivatives capable of reaction with cellulose under cold-dyeing

conditions. They were quickly followed by the less reactive monochlorotriazinyl dyes

requiring hot-dyeing conditions which were marketed as the Procion H range [38].

Direct dyes containing triazine residue patented previously by Ciba were used in the

manufacture of a complete range of monochlorotriazinyl reactive dyes under the name

Cibacron [39].


9

Introduction of the Procion MX dyes by ICI in 1956 was followed in 1957 by

the appearance of the Remazol dyes from Hoechst and the Levafix dyes from Bayer

and Drimaren range from Sandoz. Other significant developments included the

introduction of multiple-anchor dyes (Solidazol, Cassella, 1975; Sumifix-Supra,

Sumitomo, 1981), fluorotriazine containing reactive dyes (Ciba-Geigy, 1978) and

fluorotriazine containing multiple anchor dyes were manufactured by Ciba-Geigy, in

1988 [40].

ACID DYESThe acid dyes were originally so named because of most likely the presence in

their molecules of one or more sulphonic acid or other acidic group. The term applies

to an application class rather than a chemical class. Acidic groups are also being

present in many mordant, direct and reactive dyes. Acid dyes have found wide

application in dyeing wool, polyamide fibres and blends of both these fibres [41,42],

but they have to meet very high requirements as regard to their application and

fastness. Considerable attention is paid to the nontoxicity of these dyes and

intermediate products used for their synthesis, high light and wet fastness values, high

exhaustion degree in weak acid dyebaths, good leveling power.

Chemically the acid dyes consist of Azo, Anthraquinone, Triphenylmethane,

Azine, Xanthene, Ketonimine, Nitro and Nitroso compounds. Water soluble acid dyes

are also applied by direct printing on protein fibres and nylon and by vigorous

processes for preparing them; selected dyes may be printed on viscose from a urea

containing paste. Other important uses include the dyeing of leather, coating, wood,

paper, jute, straw and anodized aluminium, the colouring of food and drink, drugs,

cosmetics, insecticides, fertilizers, wood, stains, varnishes, inks, plastics and resins

and in the manufacture of toners and pigments of the lake type [43-47].

Dyeing wool with leveling acid dyes requires sulphuric or formic acid in the

dye bath along with Glauber’s salt. The dye molecules of these dyes are not firmly

bound to the dye sites in the fibre and hence on it’s they migrate. Wool is dyed in all

forms, e.g. loose wool, slubbing yarn, knitted and woven fabrics, felts and garments.

Dyes with good migration properties find their chief use on yarns and fabrics, but

dyes with inferior leveling properties and good fastness to wet processing can be used

satisfactorily on loose wool and slubbing.


10

Acid dyes are obtained from naphthalene intermediates. Due to the presence of

a number of water soluble groups in an acid dye molecule, there is every possibility

that the dye may come out on washing with water repeatedly. To increase the wash

fastness and to have better dye fibre interaction, the number of solubilising groups are

restricted and the molecular weight of the dye is adjusted in such a way that the ratio

of the solubilising groups to the molecular weight of the dye falls between one to

three hundred or four hundred approximately. Certain bulky groups are attached either

to the diazo component or to the coupling component for increasing the molecular

weight of the dye molecule.

DEVELOPMENT OF ACID DYES:

The first acid dye Orange-I (Acid Orange 20) (I) was discovered in 1876 by

Roussin, using sulphanilic acid as diazo component for wool. The coupling

component in these was 1-naphthol in Orange-I, 2-naphthol in Orange-II, N,N-

dimethylaniline in Orange-III and diphenylamine in Orange-IV. Orange-II and

Orange-IV became important commercial dyes, but in 1887 Orange-II was partly

replaced by the redder homolog Orange-R, and Orange-IV was almost entirely supere

in 1879 by the more light fast isomer Metanil Yellow of the Bayer Company.

N=N OHNaO3S

( I)

One of the oldest dye is Metanil Yellow (Acid yellow 36) (II). Because of the

basic group suitable for salt formation, the dye is not fast to acid, but it is still used

today for dyeing wool and in special areas such as leather and paper.

N=N

NaO3S

NH

( II)

In 1878 Baum [48] made an important discovery in separating the isomeric

salt of 2-naphthol disulphonic acid as G-salt and R-salt. The great difference in hue of

dyes obtained from these two intermediates showed the importance of preparing pure


11

isomers for the manufacture of azo dyes. From these intermediates Meister, Lucius

and Bruening made Orange G (III) and Ponceau 2G (IV).

N=N

HO

SO3Na

NaO3S

N=N

HO

SO3Na

SO3Na

( III) ( IV)

Other naphthol sulphonic acids were soon made and used as coupling

components for other red dyes. These dyes ranged from yellow-reds to blue-reds in

the order listed Crocein acid, G-salt, Schaeffer’s acid, R-salt, Nevile and Winther’s

acid, L-acid [49].The early important monoazo (V) and bisazo dyes have been derived

from above components.

N=NNaO3S

SO3Na

(V)

Xylene Light-Yellow 2G (VI) was made from the hydrazine and 2,5-

dichlorosulphanilic acid by M. Boeniger [50] of Sandoz in 1908.

N=NNaO3S

NNOH

CH3

Cl

ClSO3Na

(VI)

The characteristics chromophore of the anthraquinone series consist of one or

more carbonyl groups in association with a conjugated system. Anthraquinone dyes

and colourants make important contributions to a number of widely different usage

groups. The more important are acid, direct, disperse, mordant, vat, solvent, and

reactive dyes and even as pigments [51-56]. As a class, anthraquinone dyes are

generally superior to dyes of other classes.


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THE CONSTITUTION OF ACID DYES:

Azo dyes with relatively low molecular weight and one to three sulfonic acid

groups serve as acid azo dyes for dyeing and printing wool, polyamide, silk and basic-

modified acrylics and for dyeing leather, fur, paper and food. The main area of

application is the dyeing of wool and polyamide.

Disazo and polyazo dyes containing sulfonic acid groups are also frequently

used in the above applications. Many of them are marketed as substantive dyes for

cotton because of their pronounced affinity toward cellulosic fibres.

The term “acid dye” is derived from the dyeing process, which is carried out

in an acidic aqueous solution (pH 2-6). Protein fibres contain amino and carboxyl

groups, which in the isoelectric range (ca. pH 5) are ionized mostly to NH3+ and

COO–. In the acid dyebath the carboxylate ions are converted to undissociated

carboxyl groups due to the addition of acid HX (sulfuric or formic acid), which causes

the positively charged wool (H3N+ –W–COOH) to take up an equivalent amount of

acid anions X– (hydrogensulfate,formate) [57].

COO-

W

NH3+

+ H+

COOH

W

NH3+

+ X-

COOH

W

NH3X

+ F-

COOH

W

NH3 F

+ X-

Acid dyes are divided into three groups as under based on their differences in

affinity, which is primarily a function of the molecular size.

Leveling dyes are relatively small molecules, which form a salt like bond with

protein fibre. It imparts good migration properties to such dyes on wool. The

interplay between the bonded dye and the dye still in the dye bath results in

very uniform level dyeing. On the other hand they possess only poor wet

fastness, therefore the use of leveling dyes is severely limited.

Milling dyes are large volume dye molecules, for which salt formation with

the fibre plays only a secondary role and the adsorption forces between the

hydrophobic regions of the dye molecule and those of the protein fibre

predominate. The resulting bond yields good wet-fastness, but the levelness of

the dyeing is not always satisfactory because of an inadequate migration


13

property. In consequence the range of applications of milling dyes is also

limited.

Dyes with intermediate molecular size do not only form bond with wool fibre

but are also bonded to the fibre by intermolecular forces and have properties

lying in an intermediate position between those of the leveling and the milling

dyes. They are used mainly where average requirements are placed on the wet

fastness and levelness of the dyeing [58].

WOOL DYES:

The standard dyes for wool are divided essentially into four groups according

to their different dyeing behaviors.

Group A : Contains the low-priced, usually older leveling dyes with moderate light

fastness. These dyes are still used in larger quantities for cheap articles.

Group B : Includes leveling dyes, which are applied in a strongly acid bath, but

which exhibit very good light fastness.

Group C : Contains the acid dyes, which are applied in a weakly acid or neutral bath.

Group D: Contains the acid dyes with good leveling properties, intermediate

molecular sizes and for the most part light fastnesses.

In the industrial manufacture of acid azo dyes usually aniline derivatives are

used as the diazo components. The coupling components for orange to blue shades are

commonly aniline, naphthol, naphthyl amine and aminonaphthol derivatives, whereas

phenylpyrazolones are much used for preparing dyes in the yellow and orange shades.

With regard to the stability of the shade to changes in pH, that hydroxyl or

amino groups must lie adjacent to the azo group in order to form a hydrogen bond

with the later. This hydrogen bond prevents dissociation of the hydroxyl groups or

protonation of the amino groups and hence avoids an unwanted change in shade in

response to moderate pH shifts. Groups that are not in ortho position must be

alkylated or acylated.

A number of much used wool dyes belong to mono azo acid dyes that possess

no outstanding coloristic properties but that are distinguished by brilliance of shade,

very good leveling power and particularly low cost, while their wash and lightfastness

meet only low to medium requirements.

The acid monoazo dyes are classified according to the type of coupling

component.


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(1) Naphthol and Naphtholsulfonic acids as coupling components

(2) Aminonaphtholsulfonic Acid coupling components:

(3) 1-Phenyl-5-Pyrazolones as coupling components:

Especially lightfast yellow shades are obtained by using 1-phenyl-5-

pyrazolone coupling components. The first representative of the class to appear was

Tetrazine which is prepared today from 1-(phenyl-4’-sulfonic acid)-3-carboxy-5-

pyrazolone as the starting compound, obtained from oxaloacetic ester and

phenylhydrazine-4-sulfonic acid and coupling with diazotized sulfanilic acid.

For price reasons the 1-aryl-3-methyl-pyrazolones and their derivatives are

preferred to the corresponding 3-carboxypyrazolones. There is a wide range of

possible variations that dyes in this series extend from greenish yellow to reddish

orange. An example is Acid yellow 17(XI) which on wool yields a clear, yellow with

good to very good general fastness properties but relatively poor milling fastness.

NN

NNNaO3S CH3

HO

Cl

Cl

SO3Na

(XI)

POLYAMIDE DYES:

Synthetic polyamides have a structure similar to those of wool and silk but

differ in having a low acid-binding power and in their capacity to dissolve non polar

compounds. Consequently polyamide materials can be dyed with disperse dyes and

with selected acid dyes, including metal-complex dyes [59].

The choice of acid dyes for polyamides is affected by the lower acid-binding

power dyes with two and more sulfonic acid groups in the molecule which go onto the

fibre much more slowly and to a much lower saturation value than dyes with one

sulfonic acid group. Consequently, these dyes can not be mixed with one another

which lwyely compose the product ranges.

Since acid dyes on polyamide behave as they do on wool in regard to leveling

power, build-up and fastness properties, they fall into two classes:

Group A consists of acid dyes with good leveling power and low substantivity

for polyamide, they yield dyeing with reasonably good wet fastness.The main area of

application for the acid polyamide dyes of Group A is in carpet dyeing but they are


15

also used in other areas of textile dyeing where the fastness requirements are not too

stringent. For example, Acid Red 42 (XII).

N N

H2N

SO2 HO

SO3Na

(XII)

Group B contains acid dyes with lower leveling power, higher substantivity

and high wet fastness on polyamide. Many of these acid dyes with a lower leveling

power rather clearly reveal differences in fibre structure that may result from, for

example, differences in the degree of drawing (so-called streakiness) so that it is

usually necessary to add leveling and retarding auxiliaries.

Group B dyes are used almost exclusively for clothing textiles for which more

stringent requirements are placed on wet fastness. For example, Acid Blue 113 (XIII).

N N NH

SO3Na

NN

NaO3S

(XIII)

SILK DYES:

Natural silk, is a protein fibre of animal origin. It resembles wool in its

chemical structure, it can be dyed with most of the classes of dyes used for wool. The

choice of dyes depends essentially on the fastness properties required.

Selected members of the acid wool dyes are of great importance for the

dyeing of natural silk. The occasionally inadequate wet fastness of these dyeings can

be substantially improved by the proper after treatment.

Selected acid 1:1 chrome complex dyes because of their good wet and light

fastness and their very good leveling power and also 1;2 chrome complex 1;2 cobalt

complex dyes with hydrophilic groups have successfully come into use as silk dyes.

Initially the development of synthetic fibres greatly reduced the importance of

silk dyeing. Recently the processing of silk has undergone a marketed increase owing

to the growing quality consciousness of buyers, who appreciate the outstanding wear

properties of silk.

Black disazo acid dyes for nylon having excellent light and wet fastness

properties have been synthesized by Lamble et.al. [60]. Jankowski and Roland [61]


16

synthesized a violet red dye from bromamine acid with aryl sulphonamides in catalyst

suspension of 10 % sodium carbonate and copper sulphate for wool and polyamide

fibres.

Dyes for wool and polyamide fibres prepared from N-(m-tolyl) pyrolidine

coupled with diazotized 2,5-dichloro pyrolidine (XIV) which produced bright red

shades when dyed on polyamide fibres[62].

N N NAR

Me

R1

Cl

Cl

(XIV)

Where,

R = SO3H, SO2NHC2H4SO3H

R1 = H, OMe; A = Saturated heterocycle

Pyrazolone

The pyrazolone dyes possess the general structure (XV), (XVI) or (XVII);

(XV) and (XVI) correspond to the keto-enol tautomerism of 5-pyrazolone and 5-

hydroxy pyrazolone, while (XVI) and (XVII) correspond to the azo and quinine

hydrazone structures of the azophenols. It is possible to prepare the azo dyes of the

pyrazolone series by either of the methods indicated by the azo structure (XV) and

(XVI) or the hydrazone structure (XVII); these are

(a) coupling 5-pyrazolones with diazonium salts, and

(b) condensation of one mole of an α,β-diketocarboxylic acid with two moles of

an aryl hydrazine.

The colours obtainable from pyrazolone intermediates are yellow to red, and at

one time the special value of the pyrazolone intermediates was in the production of

yellow pigments and dyes, but their uses have now been extended to red and bluish-

red dyestuffs, notably in the chrome colour class.[63,64]

C

N

CH

CO

N

R N=N Ar2

Ar1

C

N

C

C

N

R N=N Ar2

Ar1

OH

C

N

C

CO

N

R N NH

Ar1

Ar2

(XV) (XVI) (XVII)


17

Among the heterocyclic compounds, pyrazole have been the subject of

considerable interest in the past decades. Pyrazoles are key structure in numerous

compounds containing this ring system, known to display diverse pharmacological

and biological activities, such as antibacterial [65,66], antifungal [67], anti-

inflammatory, analgesic and antipyretic [68-70], herbicidal, plant growth regulating

[71], protein kinase inhibiting [72], agrochemical, dyes and pigments, as well as

chelating and extracting agents. Also they are used as key starting material for

synthesis of commercial aryl/hetarylazopyrazolone dyes [73,74].

The use of heterocyclic coupling component and diazocomponents in the

synthesis of azo dyes is well established, and the resultant dyes exhibit good tinctorial

strength and brighter dyeing than those derived from aniline-based components

[75,76]. Pyrazolones are an important family of compounds for theoretical and

practical reasons. They have been widely studied as a consequence of their numerous

application, and in particular as chelating agents for solvent extraction of various

elements. Most of pyrazolone derivatives so far reported here on aryl ring at position

1, which usually diminishes their solubility.

The chemistry of pyrazolone and its derivatives has attracted much attention

because of extensive structural properties, many advantages such as high pesticide

efficiency, low human toxicity, variety of structure and application in diverse area.

They can also be used in laser materials, as 1H-NMR shift reagents, in

chromatography study, in petrochemical industry [77-81], as dyes intermediate etc.

The pyrazolone derivatives (β-diketones) are useful reagents for the extraction and

separation of metal ions [82-86].

An extensive work is being carried out on pyrazole and heterocyclic β-

diketones [87-89], due to their promising stability and easily synthesized. In many

reactions pyrazolone derivatives are also used as starting material for the synthesis of

biologically active compounds and for the construction of condensed heterocyclic

system. Moreover, particular interest was drawn due to the ability of these compounds

existing in several tautomeric forms [90-93].


18

Reactive Dyes Containing a Cyanuric Chloride NucleusCyanuric chloride contains three labile chlorine atoms which can be replaced in

succession to an amine salt or a hydroxyl compound. A simple dye containing a

cyanuric chloride can be represented as follows:

Procion H and Cibacron

N

N

N

ClX

Dye

Monochlorotriazine reactive dyes

X= Aromatic or aliphatic amine or dye with a

free amino group attached to the chlorine or

hetrocyclic residue.

Procion C

N

N

N

ClCl

Dye

Dichlorotriazine reactive dyes

The various aspects of triazine dyes are published by several workers [94,95].

Generally, there are four types of s-triazine derivatives, monohalo- and

dihalosubstituted-s-triazine with non-imino bridge links, and s-triazine with mobile

groups other than halogen. Examples of reactive dyes [96,97] based on this group are

claimed by different firms.

[97]

In 1957 ICI [98] discovered that cyanuric bromide is also suitable for the

synthesis of reactive dyestuff (XVIII).

N

N N

Br

BrNN

SO3H

SO3HHO3S

OH NH

(XVIII)

N

N

N

ClCl

NH

N NNN

SO3H SO3H

SO3H

SO3HHO3S

OH NH2


19

ICI [99] developed chloro-s-triazinyl amino residue linked through un-

coloured bridge member as reactive group having the structure (XIX).

N NH

N N

NN

N N

HN NH2

CH3

Dye

ClBr

HO3S

(XIX)

CIBA [100] had marketed direct the dyestuffs containing a monochloro-s-

triazinyl residue of the following structure (XX).

N N

NH

SO3HHO3S

OH

NN

N

NN

NH NHCOCH3

Cl

OCH3

H3CSO3H

O2N

(XX)

Two bifunctional reactive monochloro triazine azo dyes (XXI) based on

pyrazolone were synthesized and cotton fibres were dyed and the colourimetric

characteristies of the dyed fabrics were measured. They were capable of

copolymerationb with different monomers, thus inherently coloured and or stabilized

polymers were obtained [101].

NN

CH3

OH

NN

NH SO3Na

N

N

N

Cl

A

SO3Na

(XXI)

Where,

A=-Cl,-NHC6H4SO3H, -NHCH2CH=CH2,

-OCH2CH=CH2

Bayer [102] synthesized disazo pyrazole acid dyes (XXII) by reaction of

resorcinol with 2 moles of o-nitrobenzene sulphonyl chloride followed by reduction to

gives a diamine, which on tetrazotisation and coupling with 2 moles of 1-(6’-

sulphonaphthyl-2’)-3-methyl-5-amino pyrazole gave yellow dyes.


20

OSO2 SO2 O

N NN N

NN

NH2

CH3

NN

NH2

CH3

SO3HHO3S

(XXII)

Diazo acid dyes, which give bright yellowish red shade on wool from a

neutral or weakly acid bath were synthesized by Geigy [103]. Jung and Huerbin [104]

synthesized yellow diazo acid dyes (XXIII) from diphenyl sulphoxides or sulphones,

which dyed wool from a neutral to acid bath, yellow of good fastness and light

fastness.

XN

NNH2

N=NCH3

Z

Q

NN

NH2

N=N CH3

Z

Q

Y Y

(XXIII)

Where,

X=SO or SO2 and Q, Y and Z= H and Substituent atleast one of which is SO3H or

X=SO2, Y=H, Q=2-Cl, Z=5-SO3H, azo group in 4-position

2-pyrazoline-5 ones have wide applications in industry as purple and blue-

green photographic colour couplers. This class of compounds is also known as filter

dyes and electron acceptors residue, and can also act as a weak electron donor [105-

109]. 4-arylidene-1-(2,4-dinitrophenyl)3-methyl-2-pyrazoline-5-ones (XXIV) were

prepared by reaction of 1-(2,4-dinitro-phenyl-3-methyl-3-pyrazoline-5-ones with

aromatic aldehydes. Their electronic spectra and solvatochromic behavior are studied

[110].


21

NN

CH3

O

NO2

NO2

CH2 Ar

(XXIV)

Where Ar = C6H5, o-C6H4OH, p-C6H4OH, p-C6H4NO2, p-C6H4Cl and thienyl C4H3S

Methine dyes are typical donor-acceptor chromophores, and are generally

yellow to orange in colour with a high absorption intensity. In methine dyes,

substituent on the aromatic aldehydes moiety have a significant effect on the visible

absorption maxima of the dyes [111,112].

Pyrazolyl-azo dyes derived from 3-acetylamino-1-phenyl-5-pyrazolone were

prepared, characterized and ionization constant of dyes were determined by means of

dc-polarographic and spectrophotometric measurements by Ghoneim et.al. [113]. The

monochloro trizinyl reactive system is of major commercial importance in dyeing.

The presence of 1,3,5-triazine structure in the dye molecule improves their dyeing

ability and possibility for application. Dyeing performance of Hot brand, cold brand

[114], azo, bisazo [115-117], and bifunctional [118,119] reactive dyes has been

assessed on silk, wool and cotton fabrics.

Chromable acid azo dyes for wool and other protein fibres have been

synthesized by Kuthan et al. [120,121]. Blus and Kraska [122] have also synthesized

acid dyes derived from 3-Hydroxy-2-naphthanilides for use in dyeing of polyamide

fibres and wool. Luchkevich et al. [123] synthesized brown metallized acid dyes.

1H,5H-pyrazolo-[1,2α]-pyrazole 1,3,5,7(2H, 6H)-tetrone was synthesized by

the reaction between hydrazine hydrate and diethyl malonate [124]. The diethyl

malonate was used as bifunctional component in the several symmetrical bis-azo acid

dyes. The dyes were applied on wool, nylon and silk and their fastness properties

were evaluated. Pyrazolone as coupling components have been shown to be important

for the colorants from yellow to orange shades for industrial applications and show

good colour strength, luminous colours and excellent light fastness [125-127].

Derivatives of 1-phenyl-3-methyl-5-pyrazolone, 7-amino-1-hydroxy-2-

naphthalene-3-sulphonicacid,3-hydroxy-2-naphthanilide-1,4-diaminoanthraquinone


22

and group of disazo acid dyes have high light fastness properties. The relati on

between photo stability of dyes and their structure is studied by Blus Kazimierz [128].

The shifts of UV–Visible absorption maxima effected by the structural

configuration of the pyrazole dye systems were investigated and the structural effects

of the polyfunctionally substituted pyrazole dye systems on the intensity of colour and

fastness properties of the fabrics are also discribed by Shams et al.[129].

The synthesis and chemistry of nitrogen heterocyclic azo compounds have

been extensively studied, Among them pyrazolone type dyes were proved to be

excellent dyes presents a systematic and comprehensive survey of all recently

synthesized nitrogen heterocyclic dyes according to dyeing methods [130].

Easy wash off reactive dyes have been synthesized by Suwanruji and

Freeman [131]. Relatively high degrees of exhaustion and fixation were achieved for

cotton fabrics by Youssef and Mousa. [132]. Improved reactive dyeing of wool with

trifunctional reactive dyes have been achieved by Cho et al [133].

Several reactive dyes, solubilised by the incorporation of one or two cationic

dyes were synthesized by Gorgani and Taylor [134]. Each dye possessed either a

single mono or dichlorotriazine group, or a hetero-bifunctional reactive system. All

dyes fixed efficiently to nylon alkaline dyeing conditions with fixation and build up

being fully comparable to market’s leading anionic reactive dyes.

The efficiency of modifying azo dyes using pyrazolo[1,2-a]pyrazole fused

systems as the chromophoric moiety which could satisfy many economic, synthetic,

physicochemical and fastness properties. These synthesized dyes are applied to

cotton, wool and silk fabrics under the typical exhaust dyeing conditions and their

dyeing properties were investigated [135].


23

PRESENT WORKIn view of encouraging reports about technical applications of Reactive dyes

and Acid dyes, it was thought interesting to undertake synthesis and study of the

dyeing properties of some novel non azo reactive and acid dyes based on Pyrazolone.

The work is divided in two sections.

Section –I and Section-II is deals with synthesis of Hot brand Reactive and

Acid dyes on 3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-dichloro-

4-sulfo)phenyl]5-pyrazolone. General structured formula is shown below.

NN

CH3

O

Cl

ClSO3H

CH

OR

OCH3

Where R in Section -I = various cyanurated coupling components.

Where R in Section -II = p-toludino cyanurated coupling component.

The procedure followed in connection with each reactive dye and acid dyes

are as follows:

i. The reactive dyes and acid dyes are prepared under proper experimental

conditions and purified. The Thin Layer Chromatography was employed to

monitor the progress of the reaction

ii. Selected dye samples of each class are characterized by Nitrogen Elemental

Analysis, Infrared Spectroscopy and some representative Nuclear Magnetic

Resonance Spectroscopy.

iii. max of each dye in UV spectrum was recorded on UV-Thermo Scientific

Evolution 300 Spectrophotometer.

iv. Application of these dyes on cotton, silk, wool and nylon fabric according to

the class of the dye has been investigated.

v. Light fastness has been measured by the standard methods of testing (BS:

1006-1978). The rubbing fastness test has been carried out with a Crock meter

(Atlas) in accordance with AATCC-1961.

vi. The wash fastness has been measured in accordance with IS: 765-1979.


24

EXPERIMENTAL

SECTION-ISynthesis of 3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-

dichloro-4-sulfo)phenyl]5-pyrazolone [A]:

A mixture of 1(2,5-dichloro 4-sulfo)phenyl 3-methyl-5-pyrazolone (3.23 g,

0.01 mole) and 2-hydroxy-4-methoxybenzaldehyde (1.52 g, 0.01 mole) in ethanol was

refluxed on a water bath for 6 hours. The solid that separated was filtered off and

dried. Yield 86 %, M.F.: C18H14O6N2Cl2S

Cyanuration of H-acid:

Cyanuric chloride (0.01 mole,1.85 g) was stirred in acetone (25 ml) at a

temperature below 5C for a period of an hour. A neutral solution of H-acid (0.01

mole, 3.19 g) in aqueous sodium bicarbonate solution (10% w/v) was then added in

small lots in about an hour. The pH was maintained neutral by simultaneous addition

of sodium bicarbonate solution (1% w/v). The reaction mass was then stirred at 0-5C

for further 4 hours then clear solution was obtained. The cyanurated H-acid solution

was used for subsequent coupling reaction.

Preparation of the hot brand reactive dyes based on 3-methyl-4-(2-hydroxy-4-

methoxyphenyl)-methylene-1-[(2,5-dichloro-4-sulfo)phenyl]5-pyrazolone:

FORMATION OF MD1:

Coupling of A with cyanurated H-acid:

To the solution of H-acid (0.01 mole, 4.67 g), a solution of compound-A (0.01

mole, 4.57 g) in acetone was added drop wise over a period of 10-15 minutes. After

the addition, stirring was continued for 4 hours, maintaining the temperature 30-40ºC.

Sodium chloride (12 g) was then added and the mixture was stirred for an hour. The

solid dye separated out was filtered, washed with minimum amount of acetone and

dried at room temperature. Yield 84 %, M.F.: C31H18O13N6Cl3S3Na3

N Found : 8.73 % , Required: 8.81%

Following the above procedure other reactive dyes MD2 to MD12 were

synthesized using various cyanurated coupling components such as J-acid, Gamma

acid, K-acid, Laurent’s acid, Bronner’s acid, Sulpho tobias acid, Peri acid,

Bromamine acid, N-methyl J-acid, Tobias acid, Chicago acid, Koach acid, C-acid,

and N-phenyl J-acid. All the synthesized dyes are recorded in Table - 1.


25

REACTION SCHEMESECTION-I

Synthesis of 3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-

dichloro-4-sulfo)phenyl]5-pyrazolone [A]:

NN

CH3

O

Cl

ClSO3H

+

OH

OCH3OHCEthanol

Reflux NN

CH3

O

Cl

ClSO3H

CH

OH

OCH3

1(2,5-dichloro4-sulfo)phenyl3-methyl-5-pyrazolone

2-hydroxy-4-methoxybenzaldehyde

3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-dichloro-4-sulfo)phenyl]5-pyrazolone

(A)

Cyanuration of H-acid:

N

N

N

ClCl

Cl

+

NH2

HO3S SO3H

OH NH

NaO3S SO3Na

OH

N

N

N

Cl

Cl

Cyanuric chloride H-acid Cyanurated H-acid

0-5 °CAcetone

NaHCO3

Reaction of 3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-

dichloro-4-sulfo)phenyl]5-pyrazolone (A) and Cyanuration of H-acid:

NN

CH3

O

Cl

ClSO3H

CH

OH

OCH3

+NH

NaO3S SO3Na

OH

N

N

N

Cl

Cl

Cyanurated H-acid

MD1

3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-dichloro-4-sulfo)phenyl]5-pyrazolone

30-35 °CAcetone

pH 7-8

(A)


26

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

NaO3S SO3Na

OHN

NN

Cl

MD1

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NHN

NN

Cl

OH

SO3Na

MD2

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NHN

NN

Cl

OH

SO3Na

MD3

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

Cl

OH

SO3NaSO3Na

MD4


27

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

Cl

SO3Na

MD5

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

Cl SO3Na

MD6

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

Cl

SO3Na

SO3Na

MD7

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NHN

NN

Cl

SO3Na

MD8


28

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NHN

NN

Cl

O

OBr

NaO3S

MD9

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NN

NN

Cl

OH

SO3NaCH3

MD10

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

Cl

SO3Na

MD11

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NHN

NN

Cl

OH

SO3Na

NaO3S

MD12


29

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

Cl

SO3Na

SO3NaNaO3S

MD13

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NHN

NN

Cl

SO3Na

SO3Na

MD14

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

N

N

NN

Cl

OH

SO3Na

MD15


30

Table-1: Characterization of Reactive dyes based on 3-methyl-4-(2-hydroxy-4-


Dye

No.

Coupling

ComponentsMolecular formula

Mol.

Wt.

Yield

(%)

% of

Nitrogen

(Req.)

Rf

Value

MD1 H-acid C31H18O13N6Cl3S3Na3 954 84 8.81 0.42

MD2 J- acid C31H19O10N6Cl3S2Na2 852 82 9.86 0.44

MD3 Gamma acid C31H19O10N6Cl3S2Na2 852 79 9.86 0.42

MD4 K-acid C31H18O13N6Cl3S3Na3 954 81 8.81 0.46

MD5 Laurent’s acid C31H19O9N6Cl3S2Na2 836 78 10.05 0.50

MD6 Bronner’s acid C31H19O9N6Cl3S2Na2 836 83 10.05 0.40

MD7 Sulfotobius acid C31H18O12N6Cl3S3Na3 938 80 8.96 0.49

MD8 Peri acid C31H19O9N6Cl3S2Na2 836 81 10.05 0.46

MD9 Bromamine acid C35H18O11N6Cl3S2Na2Br 995 83 8.45 0.48

MD10 N-methyl J-acid C32H21O10N6Cl3S2Na2 866 79 9.70 0.44

MD11 Tobius acid C31H19O9N6Cl3S2Na2 836 78 10.05 0.47

MD12 Chicago acid C31H18O13N6Cl3S3Na3 954 80 8.81 0.43

MD13 Koach acid C31H17O15N6Cl3S4Na4 1040 82 8.08 0.49

MD14 C-acid C31H18O12N6Cl3S3Na3 938 78 8.96 0.39

MD15 N-phenyl J-acid C37H23O10N6Cl3S2Na2 928 77 9.06 0.47


31

SECTION-II

Preparation of the Acid dyes based on 3-methyl-4-(2-hydroxy-4-methoxyphenyl)-

methylene-1-[(2,5-dichloro-4-sulfo)phenyl]5-pyrazolone:

FORMATION OF MD16:

Coupling of A with cyanurated H-acid:

To the solution of H-acid (0.01 mole, 4.67 g), a solution of compound-A (0.01

mole, 4.57 g) in acetone was added drop wise over a period of 10-15 minutes. After

the addition, stirring was continued for 4 hours, maintaining the temperature 30-40ºC.

Sodium chloride (12 g) was then added and the mixture was stirred for an hour. The

solid dye separated out was filtered, washed with minimum amount of acetone and

dried at room temperature. Yield 84 %, M.F.: C31H18O13N6Cl3S3Na3

Reaction with p-Toludine:

Coupling of A with cyanurated H-acid (0.01 mole, 9.54 g) was suspended in

acetone. To this suspension p-Toludine (1.07 g, 0.01 mole) was added and the

temperature was raised to 60-65C. The mixture was stirred at this temperature for

five hours. The product obtained was filtered, washed and dried at room temperature.

Yield 82 %, M.F.: C38H26O13N7Cl2S3Na3 , N Found : 9.51 % , Required: 9.57 %

Following the above procedure other acid dyes MD17 to MD30 were

synthesized using various p-toludino cyanurated coupling components such as J-acid,

Laurent’s acid, Bronner’s acid, N-methyl J-acid, Sulfo Tobious acid, K-acid, Tobious

acid ,Gamma acid, Peri acid, Bromamine acid, Chicogo acid, Koach acid, C-acid, and

N-phenyl J-acid. All the synthesized dyes are recorded in Table –2.


32

REACTION SCHEMESECTION-II

Reaction of 3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-

dichloro-4-sulfo)phenyl]5-pyrazolone (A) with Cyanurated H-acid :

NN

CH3

O

Cl

ClSO3H

CH

OH

OCH3

+NH

NaO3S NH2

OH

N

N

N

Cl

Cl

Cyanurated H-acid3-methyl-4-(2-hydroxy-4-methoxyphenyl)-methylene-1-[(2,5-dichloro-4-sulfo)phenyl]5-pyrazolone

30-35 °CAcetone

pH 7-8

(A)

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

NaO3S SO3Na

OHN

NN

Cl

Acetone60-65 °C

NH2CH3

MD16

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

NH

SO3Na

OH

NaO3S

CH3

MD16


33

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

NH

OH

SO3Na

MD17

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

NH

SO3Na

MD18

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

NH

SO3Na

MD19


34

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

N

OH

SO3Na

CH3

MD20

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

CH3

NH

SO3Na

SO3Na

MD21

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

NH OH

SO3NaSO3Na

MD22


35

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

CH3

NH

SO3Na

MD23

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

CH3

NH

OH

SO3Na

MD24

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

NH SO3Na

MD25


36

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

NH O

OBr

NaO3S

MD26

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

NH OH

SO3Na

NaO3S

MD27

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH 3

NH

N

NN CH3

NH SO3Na

SO3NaNaO3S

MD28


37

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN

CH3

NH

SO3Na

SO3Na

MD29

NN

CH3

O

Cl

ClSO3Na

CH

O

OCH3

NH

N

NN CH3

N SO3Na

OH

MD30


38

Table-2: Characterization of Acid dyes based on 3-methyl-4-(2-hydroxy-4-


Dye

No.

Coupling

componentsMolecular formula

Mol.

Wt.

Yield

(%)

% of

Nitrogen

(Req.)

Rf

Value

MD16 H-acid C38H26O13N7Cl2S3Na3 1025 82 9.57 0.42

MD17 J- acid C38H27O10N7Cl2S2Na2 923 80 10.63 0.44

MD18 Laurent’s acid C38H27O9N7Cl2S2Na2 907 81 10.81 0.42

MD19 Bronner’s acid C38H27O9N7Cl2S2Na2 907 82 10.81 0.46

MD20 N-methyl J-acid C39H29O10N7Cl2S2Na2 937 79 10.47 0.50

MD21 Sulfotobius acid C38H26O12N7Cl2S3Na3 1009 77 9.72 0.40

MD22 K-acid C38H26O13N7Cl2S3Na3 1025 78 9.57 0.49

MD23 Tobius acid C38H27O9N7Cl2S2Na2 907 76 10.81 0.46

MD24 Gamma acid C38H27O10N7Cl2S2Na2 923 80 10.63 0.48

MD25 Peri acid C38H27O9N7Cl2S2Na2 907 81 10.81 0.44

MD26 Bromamine acid C42H26O11N7Cl2S2Na2Br 1066 79 9.20 0.47

MD27 Chicago acid C38H26O13N7Cl2S3Na3 1025 80 9.57 0.43

MD28 Koach acid C38H25O15N7Cl2S4Na4 1111 78 8.83 0.49

MD29 C-acid C38H26O13N7Cl2S3Na3 1009 77 9.72 0.39

MD30 N-phenyl J-acid C44H31O10N7Cl2S2Na2 999 76 8.82 0.47

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