Section-I: Introduction

Section-I
Introduction
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 sulphur atom of a hydroxy, an amino or a
mercapto group, respectively, of the substrate. Such covalent bonds are formed with
the amino, hydroxyl groups of cellulosic fibres, with the amino, hydroxyl and
mercapto groups of protein fibres and with the amino groups of polyamides[1]. In
general, reactive dyes are the only textile colorants designed to bond covalently with
the substrate on application. They are used for the dyeing and printing of cellulose
and to a lesser extent polyamide fibres. They are valued for their brilliance and variety
of hue, versatility and high wet fastness profiles.

The reason for such a rapid increase in demand is primarily due to the
excellent characteristics of reactive dyes, e.g. their brilliant shades, excellent wet
fastness of dyeing and simple dyeing operations which have increasingly been
accepted within the industry. However, with the growth in the usage of reactive dyes,
additional properties have been demanded by dye works and apparel manufactures[2-5]
in particular high fixation in exhaustion dyeing and high fastness to chlorine
perspiration, light and washing in the 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 colored molecular system, can be used to produce both very bright and
very dull shades of all colors. Procion dyes are greatly superior to direct cotton dyes,
which have high affinity. Because of their distinctive advantages, the procion dyes,
and fibre reactive dyes generally, have made a greater impact on dyeing technology in
the few years since their introduction than any other class of dyes in so short time.

Close attention has been paid to the fact that the existence of cations results in
some of the coloristic properties of these kinds of dyes[6]. Reactive dyes are well
known and applied for dyeing of different materials[7]. Among them triazine
derivatives have an important place.
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 Section-I: Introduction
Reactive dyes are widely used for dyeing and printing protein fibres. The
hydrophilic group of conventional reactive dyes is an anionic group, e.g. sulphonate
or carboxylate but the hydrophilic group of reactive cationic dyes is cationic[8].

Reactive dyes, the newest addition of existing dyes are the centre of attraction
in dyestuff research[9,10]. Several new reactive systems have been introduced from
time to time which covers the subject of innumerable patents and publications[11-13].
Hot brand reactive dyes are of major commercial importance in reactive dyeing[14].
It is particularly suitable in dyes for printing. On silk these dyes are reported to give
moderate to poor build-up[15, 16]. Hot brand reactive dyes have been widely considered
due to their higher fixation yield on various fibers[17]. Reactive dyes are becoming
increasingly popular for dyeing cellulosic fibres because of their wide shade range,
ease of application and excellent wet fastness properties. Improvement in the structure
of reactive chromogens, selection and number of reactive groups led to an increased
use of reactive dyes[18-20].

Reactive dyes are now a major group of dyes, though a late entry into the
family of synthetic dyes, have very soon attained a commercial status. There is no
slackening of activity in this field as seen from the large number of patent
specification and several ranges which continue to appear in the market[21-23].

Constitution 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 the presence of
aqueous alkali (DyeX + CellO DyeOCell + X ) or an activated C=C bond
which is able to add to a hydroxyl group of cellulose.
(CH=CH2 + CellOH CH2CH2OCell).

Reactive dyes are the only textile coloration 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.
hetero aromatic nucleophilic substitution and addition to an activated alkane[24-27].
Thus, the majority of reactive dyes can be distinguished in to two categories
by their reaction modes as:

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 Section-I: Introduction
(i) Nucleophilic addition-elimination dyes:

(ii) Nucleophilic addition dyes:

The general formula of a reactive dye is given as,

acbR

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 affects 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-fibre compound may have the properties of an

ester or ether; the precise nature and stability of the dye fibre bond will depend on the
reactive group.

Chromophoric system c is mainly responsible for the color of the dye.

Various types of shade can be obtained by changing the chromophoric system. From
the large number of suggested chromophoric system azo, antraquinone and
phthalocyanine derivatives have achieved greatest economical importance up to
present date. Dyestuff of these groups forms the hard core of all commercial reactive
dyestuff ranges. The widest range of shades is covered by the azo compounds, which
comprise practically every shade from greenish yellow to black. Brilliant blue and
green shades with high fastness to light are mainly from anthraquinone derivatives,
while sulfonic acids of copper and nickel phthalocyanine are used to produce
turquoise shades and in combination with yellow dyestuff to synthesize bright green
shades.
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 Section-I: Introduction

Classification of Reactive dyes

Reactive dyes can be classified into different groups as follows:

Major commercial types of reactive dyes for cellulose

Structure Commercial Firm Year of

Name Introduction

Procion ICI 1956

Procion H ICI 1957

Cibacron CIBA 1957

Remazol Hoechst 1958

Levafix P Bayer 1966

Primazin P BASF 1964

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 Section-I: Introduction
Major commercial types of reactive dyes for wool and polyamides

Commercial
Structure Year of
Name Firm
Introduction

Procilan ICI 1964

Lanasol CIBA 1966

Verofix Bayer 1970

Drimalan F Sandoz 1970

Various Reactive Systems

Reactive systems, in general, can be classified as aliphatic, aromatic and

heterocyclic reactive system as follows.

[A] Aliphatic Carrier Systems of Labile Groups

Substituted Alkane - Mono Carboxylic Acid Amides

The dyeing of cellulosic textiles with dyestuffs containing chloroacetylamino

groups (I) was first described by BASF[28], and later also by other firms. The fixation
yields of these chloroacetylamino reactive dyestuffs are also not particularlily high on
cellulosic fibers.

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 Section-I: Introduction
CIBA[29] described wool-reactive dyes containing -chloro propionylamino
groups (II) and recognized the suitabilities of -chloro propionylamino dyestuffs,
which are in most cases freely water-soluble and possess less affinity for the
continuous dyeing and printing of cellulosic fibres[30].

In a BASF patent[31] relating to -sulphonylpropionamide dyestuffs (III)

sulphonyl group is described and claimed in anthraquinone, azo and phthalocyanine
dyes.

,-dihalopropionamides (IV) were developed by CIBA[32] in cellulose

reactive dyes. The use of dichloro or dibromo propionic acid[33] is claimed in a
number of new dyes. Among other substituted aliphatic carboxylic acid, amides and
substituted isobutyric acid amides[34] are claimed as new reactive components.

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 Section-I: Introduction
Substituted Alkane - Monocarboxylates
This new reactive dyestuffs group (V) was discovered by General Aniline and
Film Corporation[35]. In such dyes saponification of propionic ester, leads to bond
formation resulting in good yield, good fixation and better fastness to washing.

Substituted Cycloalkane Carboxamide

From ethylenetetrafluoride and acrylonitrile or 1-cyano-butadiene or their
derivatives, fluoro cyclobutane carboxamides are obtained (VI) which is useful
reactive dyestuff groups. Farbwerke Hoechst and other firms[36] have claimed number
of patents related to this group.

Alkene Monocarboxamides
Reactive dyes with -chloropropionylamide groups containing acrylamide are
fairly slow in their reaction. They are less suitable for the dyeing of cellulosic
materials than for pad dyeing processes and textile printing. The crotonamide group is
even less reactive.

Substituted Aliphatic Ketones

The stability of dyestuffs containing chloromethyl or -chloroethyl aryl ketone
groups (VII) for the dyeing of cellulose in the presence of alkalies was recognized by
BASF and General Aniline[37].

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 Section-I: Introduction

- Substituted Ethyl Sulphone-Vinyl Sulphones

The following reactive systems are frequently referred to as Vinyl Sulphones
to simplify matters, though strictly speaking they are Vinyl sulphone intermediates.

For this reason, the majority of papers and patent specifications refer to a
multitude of -substituents (X), which are quite easy to eliminate, e.g. X=Cl.
Reacive dyes containing -haloethyl sulphone groups are recommended by CIBA[38]
for the dyeing of cellulose. Generally -substituents X = Cl, (Alkyl)2N, HO3SS,
H2O3PO, but primarily OSO3H is used. In the case of azo dyes the vinyl sulphone
group is usually substituted directly into the aryl nucleus of the diazo component or
that of the coupling component. In a number of patents, however bridges are included.
e.g. NH, (CH2)n, CONR(CH2)n, SO2NRAryl, CONRAryl and
NRSO2Aryl between the aryl nucleus and the vinylsulphone group. In this
connection references have been made to a large number of patents primarily from
Farbwerke Hoechst, as well Sumitomo and other firms[39,40] covering this reactive
group (VIII & IX).

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 Section-I: Introduction

In some reviews, attention is focused on the development of vinyl sulphone[41]

dyes and their general fields of applications.

- Substituted Ethylamine Derivatives

In 1956, dyestuffs containing -haloethylamines group for dyeing cellulosic
materials was described by BASF[42]. The N,N-bis-(-chloro-ethyl)-hydrazide group
(X) claimed by Sandoz is interesting from chemistry point of view. Thus all
ethylamine derivatives, containing a group in the -position, which is capable of
splitting off together with the bonding electron pair under alkaline medium, have been
mentioned as reactive groups used in reactive dyes for the dyeing of cellulose, nylon
and wool.

- Substituted Ethylamides of Sulphonic Acids

ICI[43] recognized that the water-soluble dye (XI) containing N--halo ethyl
sulphonamide groups are fixed on cellulosic fibres from aqueous alkaline medium
shades which possess excellent wet-fastness properties.

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 Section-I: Introduction
Epoxide Derivatives and Their Precursors
The group (a) and its precursor (b) are nearly always mentioned together.
Water-soluble reactive dyes of this type give dyeing with very good wet fastness
properties.

[B] Aromatic Carrier Systems

Due to equivalence of the group >N and CNO2 with regard to the
activation of halogen atoms in the ortho or para position in hetero aromatic or
aromatic rings, the aromatic carrier systems are rarely used. The virtual absence of
papers on the use of well-known aromatic carrier systems shows that they are of little
practical importance. One of the interesting systems[44] is given below (XII).

[C] Heterocyclic Carrier Systems

Pyridine Derivatives
Halogen substituents attached to pyridine or quinoline systems are not
sufficiently reactive to form covalent bonds with cellulose under normal dyeing or
printing conditions unless suitably situated electron-attracting groups are also present
in the ring to give enhanced reactivity. By condensation of amino dyestuffs with
3,5-activated 2,6-dichloropyridine[45] derivatives, easily fixed reactive dyes (XIII) are
obtained.

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 Section-I: Introduction

Pyridazone derivatives

Reacton/ Drimarine

This reactive group, has been achieved technical importance in reaction, the 6-
pyridazone substituted on nitrogen atom 1 is not an aromatic nitrogen heterocyclic; its
4,5-dihalo derivatives react in the 4-position as vinylogous carbonyl halides.

Pyridazine Derivatives
Dyestuffs containing chloropyridazine groups[46] are suitable for the printing
and continuous dyeing of cellulosic fibres with subsequent fixation in dry heat or in
steam. Tetrachloropyridazine condensed in an aqueous alcoholic medium with
1,3-diamino benzene-4-sulfonic acid, after diazotization and coupling gives the
following dyestuff (XIV).

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 Section-I: Introduction

Pyrimidine Derivatives
Pyrimidine is the most important heterocyclic carrier system.

Reactive Dyes containing a Chloropyrimidine Nucleus

(a) Dichloropyrimidine type

(b) Trichloropyrimidine type

Reacton Drimarene Z

Reactive Dyes Containing a Cyanuric chloride Nucleus

Cyanuric 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:
(a) Procion H (Cibacron)

Monochlorotriazine reactive dyes

Section-I: Introduction 12
 Section-I: Introduction
Where X = Aromatic or Aliphatic amine or dye with a free amino group attached to
the chloride or heterocyclic residue.

(b) Procion M

Dichlorotriazine reactive dyes

1,2,4-Triazine Derivatives
Halogen derivatives of not easily available 1,2,4-triazine are suitable as
reactive compounds. Finally powdered 3,5-dichloro-1,2,4-triazine condense with the
appropriate aminoazo dyestuff in aqueous solution at 0-5C and pH 4.5-6.0 forming a
reactive dyestuff, the constitution of which (substitutions position on 1, 2, 4-triazine)
is not exactly known.

Phthalazine Derivatives
Dyestuff with 1,4-dichlorophthalazine-6-carbonyl chloride, reactive
components are extremely suitable for textile printing and continuous dyeing.
Bayer[47] recognized the value of this dyestuffs group under the name Elisiane
dyestuffs.

Elisiane Brilliant Red B

Quinoxaline Derivatives
This technically important reactive principle was developed by Bayer[48],
Dupont[49], CIBA[50] and Francolor[51]. Commercial products on this basis are Levafix
E dyestuffs and the Cavalite dyestuffs.

Section-I: Introduction 13
 Section-I: Introduction

Levafix Brilliant red E-2B (Cavalite Red Y)

F. Oesterlein and K. Seitz[52] have synthesized fibre reactive disazo dye having
structure (XV) gave greenish blue dye from cotton.

Where, R = Et, Me.

R1 = H, NH2, SO3H.

CIBA[53] prepared fibre reactive azonaphtholsulfonic acid dyes (XVI) to give a

reddish brown dye for cotton.

Where, R = Cl, NH2

ICI[54] discovered the cyanuric bromide is also suitable for the synthesis of
reactive dyestuff (XVII).

Section-I: Introduction 14
 Section-I: Introduction

ICI[55,56] patented the dyestuff Procion yellow M-RS (XVIII) as well as

Procion Brilliant Orange M-FS (XIX) in the year 1954.

A. Crabtree[57] has synthesized diazo component to manufacture reactive dyes

from m-phenylene diamine-4,6-disulfonic acid and cyanuric chloride, which gives
bright red shade of the following structure (XX).

Section-I: Introduction 15
 Section-I: Introduction
Ciba Geigy[58] prepared monoazo reactive dye (XXI) for cotton to give golden
yellow shades.

Sumitomo Chemical Co. Ltd[59] prepared reactive disazo dyes (XXII) of free
acid to give reddish brown shades on cotton. Jarkovsky and Horyna[60] prepared
brown fibre reactive triazine disazo dye for dyeing cellulosic fibres (XXIII). The
presence of two o-Me groups disturbs the co-planarity of dye molecular and lowers
the substantivity of unbound dye.

Where, R = NHCH2SO3Na, NHCH2CH2SO3Na

Where, R = Cl, NH2, MeO

Section-I: Introduction 16
 Section-I: Introduction
Jin et al.[61] have synthesized scarlet dyes for cotton fabrics (XXIV).

Where, R = SO2CH2CH2OSO3H

Ciba-Geigy prepared[62] a reactive azo dyes for silk, leather, wool, polyamide,
fibers, polyurathanes, rayon, cotton and cellulose of the structure (XXV).

P. M. Mistry and J. A. Taylor[63] have synthesized navy blue reactive azo dyes
for cotton (XXVI). The compounds are characterized by good strength and ability to
build up exhaust and pad-batch dyeing to heavy depths of shade, producing colored
textiles having good resistance to washing and light.

Section-I: Introduction 17
 Section-I: Introduction
K. Seitz[64] prepared disazo reactive dyes for cellulosic fibres based on H-acid,
K-acid, S-acid or J-acid. The synthesized compound show high degree of fixation
when applied by low temperature process and produce fast navy blue dyeing and
printing cotton.

A. Tzikas[65] has synthesized reactive dyes, which gives fast navy blue shades
on cotton in dyeing and printing.

Herd et al.[66] have synthesized fibre reactive dyes (XXVII) containing a

halopyrimidinyl anchor group useful for the high color yield dyeing or printing of
hydroxyl or amide group containing fabrics in fast bluish red shade on cotton.

Mitsui Toatsu Chemicals[67] prepared water soluble reactive anthraquinone

dyes useful for dyeing cellulose fibre. The cotton knitted fabric was dyed in a dye
bath containing water and glaubers salt heated at 60C in the presence of Na2CO3 to
give uniformly dyed product with deep color, which showed color fastness to light
grade 5, color fastness to wet and light grade 4-5.

Hardina et al.[68] have synthesized novel reactive dyes for wool. This type of
reactive dyes can be prepared by diazotization of aromatic amine and subsequent
coupling reaction with secondary components. These dyes contain
SO2CH2CH2N(CH3)CH2COOH group capable of liberating reactive vinyl group in
the application dye bath. The dye showed acceptable wash fastness and light fastness.

D. Akerman and co-worker [69] have synthesized azo/hydrazo dyes (XXVIII)

derived from H-acid, with superior resistance to oxidative bleach fading.

Section-I: Introduction 18
 Section-I: Introduction

Where X = H, Cl, Br.

Y = H, Cl, Br.
SES = Sulfato Ethane Sulfonyl.

Patel et al.[70] have synthesized hot brand reactive dyes (XXIX) by coupling
tetrazotised 4,4'diaminodiphenyl sulphonamide with o-Fluoro anilino cyanurated
coupling component, and their dyeing performance on silk, wool and cotton fibres has
been assessed.

Where R= o-fluoro aniline

P. Suwanruji and H. S. Freeman[71] have synthesized bifunctional bisdichloro

triazine (bis-DCT) and tertafunctional bis monochlorotriazine/bis sulphatoethyl
sulphone [bis-(MCT/SES)] reactive dyes were applied to cotton for good color
fastness & rubbing fastness.

Mokhtari et al.[72] have synthesized trisazo heterobifunctional reactive dyes

(XXX) which gives variety of shade on cotton.

Section-I: Introduction 19
 Section-I: Introduction

Where Z =

X = -CH3, -H, -SO3Na.

Y = -CH3, -OCH3, -OC2H5

P. Petrova-Miladinova and T. N. Konstantinova[73] have synthesized reactive

triazine azodyes (XXXI) containing tertamethyl piperidine (TMP) fragment. The dyes
co-polymerized with acryl amide and acrylonitrile and the co-polymer with an intense
orange color which is stable to solvent extraction.

Where,
A1 = -NH2 -Cl
A2 = -Cl

Section-I: Introduction 20
 Section-I: Introduction
Y. W. Ho and W. H. Yao[74] have synthesized heterocyclic monoazo (XXXII)
dyes by appropriate selection of substituents in the coupling components dyes varying
in hue from yellow to blue can be obtained. The dyes were applied to polyester; their
spectral, fastness properties and color assessment are reported.

Where,
R=

Ar =

D. M. Lewis and A. A. Siddique[75] have prepared reactive dyes (XXXIII)

based on the bis (N-Carboxyl methyl amino) mono-quaternary-triazine-bis-
ethylsulphone reactive group having following structure gives good application to
cotton fabrics.

Chen et al.[76] synthesized reactive dyes containing an alkyl-thio-s-triazinyl

reactive group. It is suitable for exhaust dyeing, cold batch up dyeing and continuous
dyeing materials that contain hydroxyl group or N-group fibres.

A. A. Mousa[77] has synthesized polyfunctional reactive dyes (XXXIV)

containing bis (monochloro triazine/ sulphatoethyl sulphone) reactive system, which

Section-I: Introduction 21
 Section-I: Introduction
shows good dyeing property on silk. The twinned MCT/SES reactive system confers
relatively high fixation efficiency even at low salt/temp condition.

Where R= SO2CH2CH2OSO3Na

E. L. Gillingham and David M. Lewis[78] have prepared triazinylamino

alkylphosphonate reactive dyes (XXXV) for cotton fabrics. Which shows very high
dye-fibre fixation value (>90%) by using pad-batch-bake process.

Patel et al.[79] have been synthesized hot brand reactive dyes (XXXVI) by
coupling tetrazotized 4,4'methylene bis 2,5dichloroaniline with various m-toluidino
cyanurated coupling component for silk, wool and cotton fabrics.

Where R=m-toluidine

Section-I: Introduction 22
 Section-I: Introduction
Ruan and Weixiang[80] have synthesized tetrazo reactive dyes which are
prepared by reaction between sulfonyl containing compound and amine containing
compound and the diamine. This dye is useful for dyeing or printing of fibres.

Chu and Pingzhong[81] have synthesized blue reactive dyes (XXXVII). The
product has high color fixation rate and high binding stability.

Where X = F, Cl, NH2CH2CH2SO2CH2CH2OSO3H.

Y = F, Cl, NH2CH2CH2SO2CH2CH2OSO3H.
R1 = H or Sulfonyl.
R2 = Sulfonyl.

Chu and Pingzhong[82] have synthesized reactive brown dye (XXXVIII).

These dyes give good light fastness, perspiration resistance and soaping resistance,
and can be applied to dip dyeing, pad dyeing, jig dyeing and continuous pad dyeing of
cotton, rayon and hemp textiles.

Where R1 = H, Me, Methoxy or Sulfonic group.

R2 = H, Me, Methoxy.
Section-I: Introduction 23
 Section-I: Introduction
R3 = H, Sulfonic group or COOH.
Z = -SO2Y (on the m-position or p-position of amino group).
Y = Vinyl or CH2CH2U and U can leave under alkali condition.
M = H or alkali metal.

J. Paluszkiewicz and W. Czajkowski [83] have synthesized bifunctional reactive

dyes (XXXIX) with quinolino-s-triazine groups, and their application properties
during the dyeing of cotton fabrics were determined.

B. M. Patel and S. K. Patel[84] have synthesized bisazo reactive dyes (XXXX),

which gives a wide range of violet to red shades on cotton fibre.

Mehta et al.[85] have synthesized cold brand bisazo reactive dyes (XXXXI) for
silk, wool and cotton fibres. Exhaustion, fixation and fastness properties of these dyes
were also reported.

Section-I: Introduction 24
 Section-I: Introduction

D. N. Wadia and P. M. Patel[86] have synthesized monofunctional reactive

dyes (XXXXII) using various substituted imidazole-4-one. All the dyes were applied
to wool fabrics using various pH conditions. Wash and light fastness of prepared dyes
were reported.

Where R1= 4-OCH3; 3,4,5-OCH3; 4-OH; 4-Cl; 2-OH, 3-OCH3; 2-OH; 4-N(CH3)2;
H; 4F.

T. Kim and co-worker[87] have synthesized disazo yellow dyes of following

structure (XXXXIII). The fastness properties and K/S value are also reported.

Where R= Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl and Heptyl groups.

H. Z. Shams[88] has synthesized disazo reactive dyes (XXXXIV) using

pyrazolo[1,2-a]pyrazole fused system as chromophoric moiety. The synthesized dyes

Section-I: Introduction 25
 Section-I: Introduction
were applied to cotton, wool and silk fabrics under the typical exhaust dyeing
condition and their fastness properties were investigated.

Where

Ar =

D. R. Patel and co-worker [89] have synthesized hot brand bisazo reactive dyes
(XXXXV). These dyes were applied on silk, wool and cotton fibres. The fastness
properties, exhaustion and fixation data were also been studied.

Where R=m-nitro aniline.

D. R. Patel and co-worker [90] have synthesized cold brand reactive dyes with
quinazoline moiety (XXXXVI). All these dyes give yellow to purple color shades
with good fastness properties. The exhaustion and fixation data of all the dyes are
very good.

Section-I: Introduction 26
 Section-I: Introduction

S. H. Ungoren[91] has synthesized anthraquinone dyes (XXXXVII) from furan-

2,3-diones and their spectroscopic properties in solution and in the solid state are
reported.

F. Karci and co-worker[92] have synthesized heterocyclic disazo dyes

(XXXXVIII). The antimicrobial activity and absorption characteristics of the dyes
were also reported.

Where X= H; p-OCH3 ; p-Cl; p-CH3; m-OCH3; m-Cl; m-CH3; o-OCH3; o-Cl; o-CH3

J. Mokhtari and co-worker[93] have synthesiszed trisazo hetero bifunctional

reactive dyes (XXXXIX) based on J-acid. The dyeing properties have also been
reported.
Section-I: Introduction 27
 Section-I: Introduction

Where,
Z= SO2CH2CH2OSO3H
X= H H SO3H
Y= H CH3 H

B. Yang and co-worker[94] have synthesized tetrazine dyes with pyrazole

molecule. the reaction mechanism of formation of the 5-aryl-3-methylpyrazole[3,4e]
[1,2,3,4] tetrazines is discussed and the colors of the aminopyrazoles and pyrazolo-
tetrazine dyes in a range of solvents are also discussed.

D. R. Patel and co-worker[95] have synthesized bromine containing bisazo

reactive dyes of following structure (L). All the dyes were applied to wool, silk and
cotton fibres with fair to very good light, wash and rubbing fastness properties. All the
dyes showed good exhaustion and fixation data.

Where R=m-toluidine

Patel et al.[96] have synthesized bisazo reactive dyes (LI) from 4,4'-methylene-
bis-anthranilic acid. These dyes were applied to wool, silk and cotton fibres, which
shows moderate to very good light, wash and rubbing fastness properties.

Section-I: Introduction 28
 Section-I: Introduction

Where R=m-chloro aniline.

Patel et al.[97] have synthesized cold brand bisazo reactive dyes (LII) from
4,4'-methylene bis-(2,3-dichloro aniline). The dyed fibres show moderate to very
good fastness to light, washing and rubbing on silk wool and cotton fibres.

Literature on Quinazolinone

Quinazolinones
Quinazolinones[98] are versatile nitrogen containing heterocyclic compounds.
In 1869 Griess[99] prepared the first quinazoline derivative, 2-cyano-3, 4-dihydro-4-
oxoquinazolinone, by reaction of cyanogens with anthranilic acid. Griess apparently
recognized the bicyclic nature of the product, which he called bicyanoamidobenzene
and used until 1885 when the structure was known with some certainty[100].
Weddige[101] carried out systematic quinazoline synthesis following the observation
that the formyl and acetyl derivatives of anthranilamide lost water on heating. He
correctly interpreted this as a cyclization reaction and was first to realize the
possibility of tautomerism in the oxoquinazolines. The preparation of parent
quinazoline comes many years later when Bischler and Lang[102] obtained it by
decarboxylation of the 2-carboxy derivatives. A more satisfactory synthesis of
quinazoline was subsequently devised by Gabriel[103] who studied its properties and
those of its derivatives in greater detail.

Section-I: Introduction 29
 Section-I: Introduction
Numbering System of Quinazolinone

The nomenclature of the quinazolinone ring system is as follows.

Quinazolinone is also known as phenmiazine, benzylene-amidine, 1, 3-diaza-

naphthalene or benzo-1, 3-diazine or 5, 6-benzo-pyrimidine. The term phenmiazine
was used by Wildman[104]. The numbering shown in the structure was suggested by
Paal and Busch[105] and is one in the current use[106]. The quinazoline having a
hydroxyl group in 2- or 4- position forms a distinct class and are tautomeric[107] with
the corresponding ketodihydroxyquinazoline. Various data[108,109] indicate that
4-hydroxyquinazoline exists as an equilibrium mixture of (a) and (b) in which the
form (a) is the most favoured.

The 4-hydroxyquinazolilne tautomeric with 4-keto-3, 4-dihydro-quinazoline,

is commonly named as 4(3H)-quinazoline is also the familiar name used for the
system. Today the name 4-quinazoline has been universally accepted for 4-keto-3, 4-
dihydroquinazoline.

Synthesis of Quinazolinone
The majority of synthetic route of 4-quinazolinone essentially proceeds from
anthranilic acid or its derivatives. A number of methods may be classified into
different categories according to the type of the components undergoing
condensation.

Section-I: Introduction 30
 Section-I: Introduction
TYPE 1
This type includes condensation of
(1) N-acetyl anthranilic acid with aromatic amine in presence of
phosphorus trichloride[110-112].
(2) N-acetyl anthranilic acid with acetic anhydride affording 2-methyl-3, 1,
4-benzoxazone that is subsequently allowed to react with an amine[113-119].
(3) N-acetyl anthranilic acid with an amine in a sealed tube[120].
(4) N-acetyl anthranilic acid with formamide[121].

TYPE 2
This type includes condensation of
(1) Anthranilic acid with acid-amide[122-124].
(2) Anthranilic acid with cyanamide[125].
(3) Anthranilic acid with a compound containing N=C-Cl system[126-128].

TYPE 3
This type includes condensation of
(1) Acetanilide with urethane in presence of phosphorus pentoxide[129-131].
(2) Benzanilide imidochloride with urethane and subsequent cyclization[132-133].

TYPE 4
This type includes condensation of
(1) Anthranilamide with acid chloride and subsequent cyclization of
N-acylanthranilamide[134-136].
(2) Anthranilamide with acetic anhydride[137-138].
In addition to this many other reactions are reported which lead to the
synthesis of 4-quinazolinones[139-144].

Chromophoric potential of the 4(3H)-quinazolinone

Heterocyclic coloring matters have been known since prehistoric times in the
form of natural products such as indigo and its 6, 6'-dibromo derivative, Tyrian
Purpssle. The first commercial synthetic dye, Mauveine, discovered by Perkin in 1856
was also heterocyclic. Since that time the contribution of heterocyclic derivatives to
color chemistry has been considerable. Dyes based on the quinazoline ring system
Section-I: Introduction 31
 Section-I: Introduction
have been reported as being useful on natural and synthetic fibres[145]. Such dyes have
excellent dyeing properties including low sublimation and high thermal stability[146].

The quinazoline nucleous is the key component of a number of colored

products. The following literature shows the important role of the 4(3H)-
quinazolinone ring as a chromophore.

Azo disperse dyes such as following (LIII) containing a 4(3H)-quinazolinone

derivative as coupling component have been synthesized by Bhatti[147] gives yellow to
red shade with good fastness on natural and synthetic fibers.

Where, X = H, NO2; Y = NO2, Cl; Z = H, CN, OCH3

A. Arcoria and G. Scarlata[148] have synthesized azo dyes (LIV) with excellent
light fastness and saturation on wool, cotton, rayon and nylon.

Where X = H or COOH.

P. S. Patel and co-worker[149] have synthesized heterocyclic monoazo dyes

(LV) from 4-oxoquinazoline. Dyeing properties of these dyes on wool and silk were
assessed. Fastness properties have also been studied.

Section-I: Introduction 32
 Section-I: Introduction

Where R= Various coupling component.

H. Jung and W. Kurtz[150] have synthesized quinazoline azo pigment (LVI)

gives yellow to orange shade and useful in dyeing, printing inks, lacquers and PVC.

A. A. Cavesco[151] has synthesized fluorescent 4(3H)-quinazolones (LVII)

containing sulphonamide or carboxamidophenyl groups are reportedly used in
luminescent inks for paper.

Where R1 = H, Cl; R2 = Ph, CH3; Q = SO2, CO.

Desai et al.[152] have synthesized reactive dyes (LVIII) based on quinazoline

ring system, which gives yellow to red shade with good fastness on natural and
synthetic fibers with different coupling component.

Section-I: Introduction 33
 Section-I: Introduction

Where R = H, CH3, OCH3, NO2, Cl, Br.

Naik et al.[153] have synthesized heterocyclic monoazo dyes (LIX) for

application to viscose, silk and polyester. Dyeing and fastness properties of the dyes
were evaluated.

Where R = various coupling component.

Fadda et al.[154] have synthesized heterocyclic azo styryl dyes (LX) shows
good fastness property and variety of shade on viscose, silk and polyester.

Where R = various coupling component.

Rana et al.[155] have prepared various acid dyes (LXI) by coupling diazotized
2-Methyl-3-(2-chlorophenyl)-6-amino-4-oxoquinazoline with various coupling acid
component and their dyeing performance on silk, wool and nylon fibres has been
assessed.

Section-I: Introduction 34
 Section-I: Introduction

Where R = various coupling component

Patel et al.[156] have synthesized 4(3H)-quinazolinone based disperse dyes

(LXII), shows good fastness properties on nylon 66 and polyester fibres.

Where R= various mono and di-N-substituted aniline derivatives

Vijay H. Patel[157] and co-workers have synthesized novel heterocyclic

monoazo dyes (LXIII) by coupling with various naphthols. The dyed fibers shows fair
to good fastness to light and very good to excellent fastness to washing, rubbing,
perspiration and sublimation.

Where R = various Naphthols such as, Naphthol AS,

Section-I: Introduction 35
 Section-I: Introduction
H. S. Bhatti and S. Seshadri[158] have synthesized styryl disperse dyes (LXIV)
derived from 6-nitro substituted 3-aryl-2-methyl-4(3H)-quinazolinone. The
application properties of these dyes on polyester and their fastness properties have
been evaluated.

Where R1=CH3, C2H5; R2=CH3, C2H5, CH2C6H5

S. V. Patel and co-worker[159] have synthesized fluoran compound (LXV)

containing bromo quinazoline molecule. All these colorless fluorans develop a color
in contact with electron accepting compounds.

Where R= CH3 or C6H5, R1=Br, R2=H or Br.

S. V. Patel and co-worker[160] have synthesized quinazoline substituted fluoran

compound which shows color on contact with electron accepting compounds.

M. F. Abdel-Megeed and co-worker[161] have synthesized azo disperse dyes

containing quinazoline nucleous (LXVI). These dyes were applied to polyester fabrics
and their fastness properties were evaluated.

Section-I: Introduction 36
 Section-I: Introduction

Where Ar = -Naphthol, -Naphthol, Phenol, Resorcinol

H. D. Navadiya and co-worker[162] have synthesized mono azo dyes (LXVII)

derived from 2-phenyl-3,1-benzoxazine-4-(4H)-one. All the dyes showed good
fastness properties on nylon and polyester.

Where R= Phenol, o-cresol, m-cresol, p-cresol, o-cl-phenol, m-cl-phenol.

Patel et al.[163] have synthesized reactive dyes based on 2-phenyl-3-[4-(4-

aminophenylsulphonamido)]phenyl-4(3H)-quinazolinone-6-sulphonic acid (LXVIII)
and applied on silk, wool and cotton fibres. These dyes give good fastness properties.

Where R = Various 4-chloro anilino cyanurated coupling components.

D. R. Patel and K. C. Patel[164] have synthesized monoazo reactive dyes

(LXIX) containing quinazolinone moiety shows good dyeing as well as fastness
properties on silk, wool and cotton fibres.

Section-I: Introduction 37
 Section-I: Introduction

Where R= various 2-chloro, 4-nitro anilino cyanurated coupling components

J. T. Bilimoria and K. C. Patel[165] have synthesized monoazo dyes (LXX)

derived from 2-methyl-3-(2'-methylphenyl)-6-arylazo-4-oxoquinazoline for silk, wool
and viscose rayon fibres. All the dyes showed fair to very good light fastness and very
good to excellent washing and rubbing fastness properties.

Where R= various cyanurated coupling components

D. R. Patel and K. C. Patel[166, 167] have synthesized monoazo reactive dyes

based on 4(3H)-quinazolinone moiety. These dyes gives yellow to purple hues with
fair to very good light fastness and very good to excellent washing and rubbing
fastness properties. Some of the dyes showed good antimicrobial activity.

Section-I: Introduction 38
 Section-I: Introduction

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Section-I: Introduction 44
 Section-I: Introduction
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166. D. R. Patel, K. C. Patel, J. Serb. Chem. Soc. (2010) (Accepted-In press).
167. D. R. Patel, K. C. Patel, Dyes Pigm. (2010) (Accepted).

Section-I: Introduction 45