Five and Six-Membered Heterocycles Tawfik A

Home , Aromatic amine

78 Egypt.J.Chem. Vol. 61, No.5 pp.897- 937 (2018) A Review on Synthesis of Nitrogen-containing Heterocyclic Dyes for Textile Fibers - Part 1: Five and Six-membered Heterocycles Tawfik A. Khattab1* and Mohamed Rehan2 1Dyeing, Printing and Auxiliaries Department, Textile Industries Research Division- National Research Centre, 33 El-Buhouth Street, Dokki, Cairo 12622, Egypt. 2Department of Pretreatment and Finishing of Cellulosic Fibers, Textile Industries Research Division National Research Centre, 33 El-Buhouth Street, Dokki, Cairo 12622, Egypt.

HE SIGNIFICANCE of heterocyclic dyestuffs has recently increased due to their deep Thues and brightness, high color strength and better colorfastness compared to benzene analogous dyes. In this review, we give details outlining the synthetic approaches of all recently synthesized nitrogen-containing five and six-membered ring heterocyclic dyestuffs and their dyeing efficiency on textile fibers.

Keywords: Nitrogen heteroatom, Heterocyclic, Dyes, Synthesis, Dyeing, Fabric.

Introduction to their structure or according to end-use application on a certain substrate [23]. For instance, the disperse The former synthetic dyestuff, Mauveine, dyestuffs are characterized by a variety of chemical was recognized by Perkin in 1850s [1]. Dyes structures such as monoazo 1 [24], anthraquinone 2 have become indispensable tools for a variety of [25] and disazo 3 [26] structures (Fig. 1) and they are applications [2]. For instance, they act as colorants applied on hydrophobic substrates such as polyester for plastics, paper, ceramics, coatings, constructions, fibers. textiles and other highly sophisticated technology purposes [1-8]. Dyes are also used in sensors, inks, Heterocyclic-based materials are pervasive in tinting, adhesives, beverages, cosmetics, foodstuff, various fields of life sciences [27-35]. Heterocyclic polymers, optical data storage, leather, and wax dyes have been utilized in many fields, such as inkjet biomedicine [9-22]. Dyes that are employed for printing, photovoltaics, photography, digital optical textiles dyeing often come with particular properties storage, photodynamic therapy, bioimaging [2, 6, that include color fastness to sublimation, light, 12, 36-38]. Azo dyestuffs are now used to generate wash, perspiration and rubbing. Dyes used in textile nearly the whole range of color shades. For instance, industry can currently be described as mature. the anthraquinone derivatives of azo dyes are usually Nonetheless, it stays a vibrant and challenging employed for red, blue, violet and turquoise shades, field which necessitates a continuous production while other azo derivatives are used mostly to of novel materials due to the fast changing global manufacture yellow shades [2]. A long-term target of customers’ requirements. Several types of dye used dyestuffs research has been to merge both brightness today were recognized in 1800s [1, 2]. However, and colorfastness properties of anthraquinone-based the oil crisis in 1970s led to a sharp increase in the dyestuffs with the color strength and low cost of cost of raw materials for dyestuffs. This generated azo-based dyestuffs. This target is currently being a force toward lower cost dyestuffs by enhancing recognized with heterocyclic-based azo dyestuffs, the efficiency of the procedures and by replacing which can be divided into two major classes dyestuffs of low tinctorial strength, such as depending on the different chemical structures of the anthraquinone-based dyes, by tinctorially stronger heterocyclic coupling moieties and the heterocyclic dyes, such as heterocyclic-based benzofuranone and diazo moieties. All heterocyclic coupling moieties azo dyes. These subject matters are still significant that offer commercially significant azo dyestuffs and continuing, as are the modern matters of enclose mainly nitrogen heteroatom, such as indoles merchandise safety, quality, and environmental 4, pyrazolones 5, and in particular pyridones 6; protection [2]. Therefore, a variety of dyes have (Fig. 2) which afford yellow to orange shades on been reported. Dyestuffs can be classified according various substrates [2, 39].

HO O NH2 O

N N N R N O2N O CH3 O O NH2 C.I. Disperse Yellow 5 Turquoise R=alkyl 1 2

CH3 N N N N CN

HO N O 3 CH3 Fig. 1. Chemical structures of the disperse dyestuffs. CH R 3 R' R' N HO N N HO N O 4 R 5 Ar 6 R

Fig. 2. Chemical structures of the azo dyes contain mainly nitrogen heteroatom.

azopyridones are usually exist in the hydrazone Many dyes of yellow shade were of form. Typical examples include azopyrazolone azopyrazolones, however those have currently been C.I. Acid Yellow 23 7 and azopyridone 8 [40, 41] mostly replaced by azopyridones. Azopyridone (Fig. 3). In this review, the five and six-nitrogen dyestuffs of yellow shades are characterized containing heterocyclic dyes will be divided by better brightness and color strength, and according to the number of atoms building the commonly possess better colorfastness properties heterocyclic ring and the number of nitrogen than azopyrazolones. Both of azopyrazolones and heteroatoms included in their molecular structure.

HO3S

Cl CH3 N N COOH N CN H N N H O N O N O

7 8 CH3 SO3H Fig. 3. Chemical structures of azopyrazolone (7) and azopyridone (8). Egypt.J.Chem. 61, No.5 (2018) 899 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

Dye classes exhaustion of chromium on fibers, reducing water The sort of dyestuff used to dye technical pollution by chromium [44]. textiles depends on the fiber characteristics, the target color, color strength, ease of coloration and Basic dyes colorfastness properties demanded by end-users. Basic dyes are cationic colorants with Some dyestuff types will dye some different substantivity for acrylic, polyester, and nylon fibers, but practically one fiber will dominate. For fibers on which basic dyes can introduce brilliant instance, disperse dyestuffs are mostly employed colors. Basic dyes can be used to dye proteinic to dye polyester fibers, although they can also be and cellulose acetate fibers, but their light fastness used to dye nylon, acrylic, and cellulose acetate on hydrophilic fibers is poor. The ionic attraction fibers, but with limits upon the color strength and among the basic dyestuff and the sulfonic acid color fastness properties [2, 42]. active sites in acrylic fibers is strong, which affords excellent colorfastness to wash. The close- Acid dyes packed physicochemical character of acrylic fibers Acid dyestuffs are anionic in nature with and the dye-fiber strong bond can lead to weak substantivity to proteinic fibers, such as wool, migration and leveling, but introduce excellent silk, nylon or any further garments containing color fastness against light. Acrylic fibers differ basic functional groups. Acid dyestuffs are broadly in their dye-ability due to the different usually applied from an acidic or neutral dye-bath. quantities of different monomers employed with Acid dyes can be printed onto wool, silk, nylon, polyacrylonitrile that adjust the requested glass and other fibers employing traditional printing transition temperature of the fiber. Print fixation thickeners followed steam fixation, washing, and is carried out by steam followed by washing, and then drying. Acid dyes enclose acidic functional finally drying [45]. groups, generally sulfonates. Wool, silk and nylon fibers enclose amino functional groups which is Azoic dyes protonated in acidic dye-bath to present active Azoic dyes are generated within the fiber + - typically by adsorption of an aromatic hydroxyl- basic sites (- NH3). The acid dye anion (-SO3 ), is therefore substantive to the fiber and is adsorbed, bearing substance, such as naphthol as the azoic creating a salt-like bond with the fiber active coupling active agent followed by azo-coupling basic sites. Monosulfonated acid dyestuffs can process with a stabilized aromatic diazonium be adsorbed to a higher level than di-, tri-, or salt to introduce a colored insoluble dye with tetrasulfonated acid dyestuffs because the amount azo functional group. The application technique of active basic sites on the fibers is restricted by must be performed with care as the ending color the fiber structure. Therefore, the color strength is is only achieved after soaping off to eliminate usually higher with monosulfonated acid dyestuffs any remained traces of the azoic starting on wool which is characterized by higher active components located on the fiber surface that may basic sites than nylon and silk. However, the acid provide inferior colorfastness to washing and dye solubility in water increases upon increasing rubbing. Although azoic dyes are inexpensive the number of sulfonate groups [43]. to introduce red and black colors because their color range is currently more restricted as some Mordant dyes diazo compounds prepared from certain aromatic Chrome mordant dyestuffs are the only amines have been inhibited due to their probable category of mordant dyes with commercial carcinogenic character [46]. importance. They are applied in exhaustion dyeing onto wool or irregularly nylon fibers with high Direct dyes color fastness. The fibers are typically dyed by the Direct dyestuffs were recognized as the former afterchrome technique in which a chrome dye is category of synthetic dyestuffs to be applied on applied on fiber followed by additional treatment cotton fibers directly without mordant. They at pH 3.5 in a next bath be full of potassium or are sulfonated diazo, trisazo or polyazo anionic sodium dichromate. The absorption of dichromate colorants with substantivity to cellulosic fibers. anions results in the development of a 1 : 1 and/ Direct dyes containing stilbene, oxazine, copper or 1 : 2 chromium metal complex dyestuff complex, thiazole and phthalocyanine chemical within the fiber, which results in some troubles frameworks were also employed. They have in batch-to-batch reproducibility of shade. Low lower color brightness than acid and basic dyes. chrome dyeing processes can encourage complete Phthalocyanines are employed for highly bright Egypt.J.Chem. 61, No. 5 (2018) 900 TAWFIK A. KHATTAB AND MOHAMED REHAN blue and turquoise-blue colors of excellent the hydrolyzed reactive dyestuff residues. The colorfastness against light. Copper-complex high water solubility generates ecological trouble direct dyestuffs also display high colorfastness in waste water treatment plants as usually only to light. An electrolyte, sodium sulphate, is 0-30% of the hydrolyzed reactive dyestuffs can typically included in the dye-bath to defeat be eliminated [48]. the negative charges on cellulose fiber surface which otherwise would resist reaching direct dye Sulfur dyes anions. The electrolyte sodium ions neutralize the Sulphur dyes are produced by heating a variety negative charges at the fiber surface, permitting of aromatic diamines, nitrophenols,…etc, with the dyestuff anions to be adsorbed and held onto sulphur and sodium sulphide. Sulphur dyestuffs the fiber. Direct dyestuffs are generally linear and are formed in an water-insoluble pigment form planar molecular frameworks permitting multiple with no substantive ability to cellulosic fibers. linkages to cellulose polymer chain units, Treating sulfur dyes with a reduction agent such however the attraction forces among dyestuff as sodium sulphide or sodium hydrosulphide in molecule and fiber are comparatively poor when presence of an alkali transforms the sulfur dye the dyed fiber is soaked in water. Accordingly, the molecule into the reduced soluble leuco form colorfastness to wash is medium to poor, however with high substantive character to cellulose. Once the colorfastness to light ranges between excellent absorbed onto the fiber, the dye molecule is then to poor relying on the chemical structure of the oxidized, typically using hydrogen peroxide, back dye [47]. to the water-insoluble pigment form. Soaping off, after dyeing, is significant to guarantee the Reactive dyes highest colorfastness to washing and rubbing. Reactive dyestuffs are an extremely Sulphur dyes are cheaper than numerous other significant category of colorants for cellulosic dyes, however, the waste water from dyeing may and proteinic fibers. Although they are quite necessitate particular treatments before discharge expensive, they give a broad series of bright into waste water treatment plants [49]. colors of high colorfastness to washing. This is because during the fixation procedure, Vat dyes typically performed in alkaline environment, Vat dyestuffs are water-insoluble, however strong covalent bonding is created among dye they enclose two or more ketone (>C=O) and fiber. Reactive dyestuffs may interact via functional substituents separated by a conjugated substitution reaction of monochlorotriazinyl- or molecular structures of double bonds that are dichlorotriazinyl-based reactive dyestuffs or reduced to the water-soluble enolate (>C-O-) leuco via addition reaction of vinylsulfone-containing form. The dye application technique contain three reactive dyes. Recent developments resulted in the steps, including, alkaline reduction by sodium production of homobifunctional-based reactive hydroxide and sodium hydrosulphite, increasing dyestuffs, such as two monochlorotriazine; and substantivity of leuco form to the fiber, assisted heterobifunctional-based reactive dyestuffs, by electrolyte, such as sodium sulphate, and such as monochlorotriazine in combination with wetting, dispersing and levelling agents, followed vinylsulfone in order to enhance the dye bonding by reproduction of the insoluble vat dye within on the fiber in the alkaline environment (50-70% the fiber via oxidation using hydrogen peroxide. for mono-reactive group and 80-95% for di- The dyed fibers are then thoroughly washed off to reactive functional groups). The dye application remove any surface dye. Vat dye molecular structure techniques on fibers include exhaustion, cold pad- range is between indanthrones, flavanthrones, batch or continuous pad-steam. Reactive dyes pyranthrones, dibenzanthrones, acylaminoanthra- may hydrolyze in water and in presence of alkali. quinones, carbazoles, azoanthraquininones, During the dyeing process, some hydrolyzed indigoids and thioindigoids. Vat colorants are reactive dyestuff molecules are absorbed by comparatively costly but present excellent color the fiber because it acts as a substantive direct fastness properties on cellulose [50, 51]. dyestuff, as but with less colorfastness to wash Disperse dyes than the reactive dyestuff that is covalently Disperse dyes are water-insoluble colorants of bounded to the fabric polymer chain units. small size molecular structure with substantivity Therefore, the dyeing steps are usually followed for hydrophobic fibers and are generally applied by an extensive wash-off process to eliminate as a fine aqueous dispersion. The key chemical

Egypt.J.Chem. 61, No.5 (2018) 901 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ... categories are aminoazobenzenes, anthraquinones, pigments are such as carbon, antimony oxide, nitrodiphenylamines, styryls, quinophthalones, titanium, iron and zinc, while organic pigments and benzodifuranones. Disperse colorants are include a wide range of chemical structures such pulverized using a dispersing agent. Disperse as azo compounds, anthraquinones, dioxazines, dyestuffs are basically nonionic compounds indanthrones, perylenes, quinacridones, usually attracted to hydrophobic fibers, such as copper phthalocyanines, heterocyclic nickel polyester and cellulose acetate. The aqueous complexes…etc. The pigment particles are solubility of disperse dyes is low but increases at ground down to a fine state and stabilized by high temperature, and consequently raises dyeing dispersing agents and stabilizers. Numerous rate. The dye solubility can also be increased high performance textiles are printed by upon employing levelling agents and carriers. pigments in order to afford the high performance Therefore, the high temperature pressure disperse requirements claimed by end-users [53-55]. dyeing at 130°C, followed by dry thermofixation are usually used. To reduce potential troubles Heterocyclic dyes containing 5-membered associated with the residual of disperse dyes on ring with two nitrogen heteroatoms the fiber surface after dyeing which result in poor Diethyloxalate was reacted with color fastness, reduction clearing is employed methylamine to afford 9 which then interacted after dyeing using sodium hydroxide, sodium with phosphorus pentachloride to afford 10 hydrosulphite and a surfactant [52]. [56] followed by nitration and treatment with ammonia to produce 11. Compound 13 Pigments [57] was prepared by treating 12 [58] with Pigments are water-insoluble synthetic or chlorocyanogen (Scheme 1). natural organic or inorganic materials. Inorganic

PCl5 (C2H5O)CO + 2CH3NH2 (CH3NH)2CO 9

NO2 N N 1.HNO2 N Cl 2.NH3 N NH2 10 CH3 CH3 11

NC NC CN N NC Cl

H2N NH2 NC N NH2 12 H 13 Scheme 1.

Imidazole dyes of red to violet shades with corresponding diazonium salt followed by azo- moderate colorfastness, derived from compound coupling with N-benzyl-N-ethyl-m-acetamide 11 were prepared. Bright red dyes having high aniline to afford 14 [59] (Scheme 2). Such absorptivity and good light and sublimation dyes possess poor light fastness which can fastness on polyester and polyamide fabrics be improved by alkylation of imidazole ring were prepared from the imidazole derivative to produce 15 (Scheme 2) and resulting in 13 [59] which was diazotized to produce the bathochromic shift.

Egypt.J.Chem. 61, No. 5 (2018) 902 TAWFIK A. KHATTAB AND MOHAMED REHAN

NC NC N NC C2H5 HCl/NaNO2 N couple N - + N N N NC N NH2 NC N N2 NC N 13 H H 14 CH3CONH NC C2H5 N N N N (CH3)2SO4 NC N K2CO3, H2O, acetone CH3 CH CONH 15 3 Scheme 2.

Blue imidazole diazo dyes 18 were prepared to the coupler nitrogen atom is diazotized and from 13 [59] (Scheme 3) using couplers such transformed into diazocyanide, which was then as 1-naphthylamine giving 16, followed by reacted with o-phenylenediamine to afford diazotization procedure and azo-coupling 2-benzimidazolylazo dyestuff. Reaction of of the intermediate dyestuff 16 and lastly, 19 with hydrazine or its derivatives produced the diazo dyestuff 17 is alkylated. Coupler 5-aminopyrazoles 20. Reaction of isoxazole 21 containing amino group at the para position with hydrazine produced 22 [60].

NC NC N N azo-couple azo-couple N N NH2 NC N NH2 NC N H H 16 13

NC N (CH3)2SO4 N N N N N(C2H5)2 NC N H CH3CONH NC N 17 N N N N N(C2H5)2 NC N

CH3 CH3CONH 18

O R R CH2CN NH2NH2 R CH2CN N N N NH 19 NH2 2 H 20 O N CH 2 CH3 NO2 3 NO2 NH NH N 2 2 CN CH N 3 O N N NH2 NH2 21 H 22 Scheme 3. Egypt.J.Chem. 61, No.5 (2018) 903 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

Cyanopyrazoles 24 [61-63] (Scheme 4) tetracyanoethylene with hydrazine [64]. 4-Aryl-5- was obtained by condensation of 23 or its amino-3-trifluoromethylpyrazoles were prepared C-alkyl or C-aryl analogues, with hydrazine or from the properly substituted hydrazine and its derivatives. Compound 26 (Scheme 4) can β-ketonitrile. Aminopyrazoles with substituted be synthesized via reacting 25 with hydrazine nitrogen heteroatom were synthesized by reacting or substituted hydrazines. 5-Amino-3,4- phenylhydrazine with acrylonitrile followed by dicyanopyrazoles can be obtained via reaction of dehydrogenation of the produced pyrazoline.

R CN(COO Alkyl) R CN + NH2NHR1 N N C2H5O CN(COO Alkyl) NH2 R, R1= H , a lkyl, aryl 23 R1 24

R2S CN R2S CN R2= alkyl + NH2NHR3 N R2S CN N NH2 R3= H, alkyl, aryl 25 R3 26 Scheme 4.

Yellow to violet cyano dyes 27 for dyestuffs upon using 3’-(N,N-dialkylamino)- hydrophobic fibers were prepared from the acylanilide-type as couplers. Yellow dyestuffs 5-aminopyrazole derivative 24. Also 27 were are produced when 5-aminopyrazoles are prepared by diazotization and coupling of 28 diazotized and azo-coupled with 3-cyano- to give the corresponding bromo intermediates 4-alkyl-6-hydroxy-2-pyridone and indole 29 which were then converted to 27 via couplers. Acid dyestuffs are synthesized from reaction with metal cyanides [12] (Scheme 5). these diazo moieties with aromatic amine Bright red dyestuffs with good light fastness on couplers which enclose N-(sulfatoalkyl) polyester fibers are produced in this series of functional groups [65].

R Br

N N NH2 28 R1

R CN R CN R Br azo-coupling CuCN N (low yield) N N N N N N N NH2 N (high yield) N coupler coupler R1 24 R R 1 27 1 29 Scheme 5. Egypt.J.Chem. 61, No. 5 (2018) 904 TAWFIK A. KHATTAB AND MOHAMED REHAN

H3C H R H2N N N O O N H2C CH2 + NH3 O NH O CO 2 30 31 R 32 Scheme 6.

The prazolone 32 (Scheme 6) were produced Reaction of diacetonitrile, which were from 31 which were prepared from the diketene obtained by reaction of acetonitrile with sodium 30. Coupling aniline with 32 afforded the metal, with hydrazine afforded the iminopyrazole hydrazonoprazolone dye 33 [66] (Fig. 4). 34 (Scheme 7).

N N O CH3 H N N 33

Fig. 4. Chemical structures of the hydrazonoprazolone dye.

H3C Na NC NH2NHR 2 NC CH3 N NH N NH R 34 Scheme 7.

Kurtz and Gold described the synthesis of to cyanoallene and reacted with substituted 5-aminopyrazole from propargyl chloride via hydrazine to create the hydrazone form of reaction with hydrogen cyanide to produce cyanoacetone. This is followed by ring closure to propargyl cyanide which was isomerized yield 5-aminopyrazole 35 (Scheme 8).

H2 Cu-catalyst H2 HC C Cl + HCN HC C CN H2C C C CN H

H3C H3C CH2 NH NHR 2 N CN N NH N NH2 R R 35 Scheme 8. Egypt.J.Chem. 61, No.5 (2018) 905 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

5-aminopyrazoles can be azo-coupled in an Imidazole was used as coupling component to acidic environment to provide azo dyestuffs 36- give 39 which was quaternized to 40 followed by 38 (Scheme 9). They are significant to produce reaction with secondary amine [67] leading to the very bright greenish-yellow shades of good corresponding azacyanine dyes 41. Dyestuffs 41 light fastness and good migration, especially on were characterized by brilliant red shades on acrylic wool, polyamide and acrylic fibers. fibers with good light fastness and good migration [68] (Scheme 10).

Cl NH - NH2 2 X O CH3 N N + HO3S N N H3C N C N N N N H2 CH3 Cl 37 36 CH3 CH3 H3C - X N N N H3C + N

H3C 38 N H Scheme 9.

+ NH NH (CH3)2SO4 + N2 Cl N N Cl N N 39 CH3 CH3 R1 HN N N R R1 N N Cl 2 N N N R2 N + N + - X 41 CH3 40 CH3

Scheme 10.

Pyrazol-3-ones were synthesized using Disperse dyes of chemical frameworks with biacetyl and primary aromatic amines [69]. suitable substitution patterns; have fairly Dyes 42 and 43 were obtained by conventional good characteristics on polyester fibers. Best azo-coupling (Fig. 5). The reactivity of outcomes were recognized with azo-metal pyrazol-3-ones are less than that pyrazol- complex derivatives in dyeing of wool fibers. 5-ones in the azo-coupling process [70]. Comparison among pyrazolone isomers is Longer reaction periods (2-3 hours instead of highly favorable to pyrazol-5-one for which 30 minutes) and higher pH environment (7-8 colorfastness properties and tinctorial strength instead of 2-3) are required. The pyrazole dye always have higher levels than pyrazol-3-one 42 offered greenish-yellow shades with low [71]. degree of saturation and decreased lightness. Egypt.J.Chem. 61, No. 5 (2018) 906 TAWFIK A. KHATTAB AND MOHAMED REHAN

A N N OH CH3 N A N N H3C N H N O N 42 43 Y A= aryl, (arylazo)aryl, anthraquinonyl

Fig. 5. Chemical structure of the Pyrazol-3-ones.

Diazotized 44 was subjected to azo-coupling Dye 48 was reacted with cyclohexylamine or with 45 in sodium acetate buffered solution to lysine using ethyl chloroformate as an activating form 46. Reaction between arene diazonium ions agent, to produce and amide compound that can and 46 in presence of sodium hydroxide produced then be reactively dyed on wool and nylon 6.6 asymmetrical 3-cyanoformazans 47 (Scheme 11). affording colorfastness properties which are far superior to those predictable for traditional acid The derivatives of compounds 46 and 47 dyeing using carboxy-based derivatives. This were evaluated as direct, acid and basic dyes. The indicates considerable fixation of the dye onto the coloration features on cellulose, wool and nylon fiber [73]. were mainly satisfactory. All dyeings have very good colorfastness to light, although colorfastness Yellow acid dyes 49 and 50 (Fig. 7) derived to wash was moderate [72]. The hydrazone dye from I-phenyl-3-methyl-5-pyrazolone, were 48 (Fig. 6) was synthesized via diazotization of synthesized by diazotization of the proper amines m-aminobenzoic acid followed by coupling with followed by azo-coupling with the pyrazolones in N-phenyl-2-methyl-5-pyrazolone. an alkaline environment at 0-5ºC.

O O H azo-coupling 44 N Ph N C N Ph N H H2 H (CH3COONa) N N R 45 46

NH + 2 Ar = C6H5, C6H4CH3-p, ArN2 N N Ar R= N H C6H4Br-p, C6H4NO2-p, (NaOH) N N R NH C6H4OH-o, C6H4COOH-o N 47 Ph 44 Scheme 11.

48 a) X= OH COX b) X= HN O N N c) X= OCH CH N N 2 3 H CH3 Fig. 6. Chemical structure of the hydrazone dye.

Egypt.J.Chem. 61, No.5 (2018) 907 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

CH3 Y N N N A= H, NO2,HNO2S z O N X= H, CH3, OCH3, SO3Na 49 A Y= H, CH3, SO3Na CH3(OCH3)

Z= H, SO3Na, O2SHN , O SHN CH 2 N N 3 SO3Na N SO3Na O N

SO3Na NHO2S 50 Fig.7. Chemical structure of yellow acid dyes.

Dyes containing arylsulfonamide moiety can The copper azo dye complex 51 (Fig. 8) was be applied on polyamide and wool fibers from obtained by condensation of benzene sulfonyl weakly acidic dye-bath as the arylsulfonamide chloride with I-(3’-amino)-phenyl-3-methyl-5- functional groups increase their affinity for pyrazolone in water in acidic medium at l0-15°C polyamide giving better leveling, and also in the first stage, and 40-45°C in the last stage. The enhance the colorfastness to perspiration and azo-coupling process was performed via coupling wet rubbing. Lower light fastness was observed the diazo components and quinone diazides with with derivatives of naphthylaminesulfonic I-(3’-N-benzenesulfonamido) phenyl-3-methyl- acid and also for derivatives of o-anisidine- 5-pyrazolone in alkaline medium at 0-5°C. 4-sulfonic acid. Dyes derived from toluidine To produce 1:1 copper-azo dyestuff complex, sulfonanilide sulfonic acid show very high light the alkaline dye solution was reacted with (Cu +2 fastness [74]. (NH3)4) at 35-40°C for 34 hours.

H C SO3Na 3 N N X N L= NH , H O N 3 2 O O X= SO3Na, H, Cl, NO2 Cu SO NH 51 2 SO3Na SO2NH L

Fig. 8. Chemical structure of the copper azo dye complex.

Egypt.J.Chem. 61, No. 5 (2018) 908 TAWFIK A. KHATTAB AND MOHAMED REHAN

Orange and red dyes 51 were very appropriate aminomalonamide and ethyl orthoformate for dyeing polyamide and wool fibers from [77]. The C14 labeled analogue has also a weakly acidic dye-bath solution. The been synthesized from C14 carbonyl labeled arylsulfonamide group increased their affinity aminomalonamide and ethyl formiminoester to polyamide and has beneficial influence on the [78]. The interaction of 55 with 56 afforded colorfastness to perspiration, light and rubbing 57 which reacted with nitrous acid to give 58 [75]. followed by reduction with sodium dithionite to afford 52 via formation of the intermediate Diazotization of the arylamine 53 and coupling amine 59 (Scheme 13). Dyestuffs were to the imidazole 52 in acidic medium produced the highly liable to degradation under traditional corresponding azoimidazole dyes 54 (Scheme 12). coloration conditions as disperse dyestuffs on Compound 52 was synthesized by dehydration synthetic fibers to give dull yellow to brownish- of 4(5)-hydroxy-5(4)-imidazole carboxamide yellow shades. Thus, they have no value in this [76] which can be prepared via reaction of regard [79].

NC H N N OH 52 A N N CN HO N H N 54 H X

X= H, OCH3, Cl, Br, CN, NO2 A= Y NH2 Y= H, OCH3, NO2, NHCOCH3 Z= H, Cl, Br, CN 53 z

Scheme 12.

O O H NC N H + NC C OH H NH2 H O O 2 55 56 57

NH 2 H O O N H 52 NC NC N H H 59 O O NOH 58 Scheme 13.

Iron complexes of monoazo mordant pyrazole fastness on wool dyed with afterchrome dyes. In dyes (e.g. Mordant Orange 37 (60) (Fig. 9), case of other 1:2 iron metalized dyestuffs, [80] the Mordant Red 7 and Mordant Brown 15), were light fastness of iron complexes is less than that of produced by treating dyed fibers with iron salts to Cr analogs, but commonly much better than the afford brown to black shades with increased light corresponding metal-free analogs [81].

Egypt.J.Chem. 61, No.5 (2018) 909 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

- 3- SO3 H3C N N N N O O + Fe 3Na O O N N N N - CH3 O3S 60 Fig. 9. chemical structure of the Mordant Orange 37.

Compound 61 was reacted with cyanuric Cyanuric chloride was reacted with AH chloride followed by diazotization [82] and azo- to produce 64 which was then reacted with coupling with N-(4’-sulfo)-phenyl-3-methyl-5- 1,3-phenylendiamino-4-sulfonic acid. Without pyrazolone (SP), to afford 62 which was reacted isolation of products 65, after their diazotization as basic chromophore with AH to produce 63 [83] and azo-coupling with (SP), dyes 63a-c were (Scheme 14). obtained (Scheme 15).

Cl N Cl H Cl N N SO Na H2N SO3Na 3 + N N N N NH 61 NH2 2 Cl Cl H N NaNO2/HCl Cl N SO3Na CH3 N N N N H N Cl N N SO Na Cl HO N SP 3 pH= 7.5 N N + N2Cl 62 Cl

SO3Na + AH

H N A N SO3Na CH3 N N N N N Cl HO N

63a-c SO3Na Scheme 14 . Egypt.J.Chem. 61, No. 5 (2018) 910 TAWFIK A. KHATTAB AND MOHAMED REHAN

Cl N Cl A N Cl H N N SO3Na m-PDA A AH + N N N N N N NH2 Cl 65 Cl 64 Cl 1) NaNO /HCl A= NHC6H4SO3H (a) 2 A= NHCH2CH=CH2 (b) 2)SP pH= 7.5 A= OCH2CH=CH2 (c) 63a-c Scheme 15.

A color shift to blue-greenish color was Compound 66 (Fig. 10) as potential monitored for 63b (A= -NHCH2CH=CH2) substitute for benzidine, has been synthesized and to blue-reddish color for 63c (A= via interaction among urea and para-

-OCH2CH=CH2) compared to the basic dye 63a phenyldiamine in water. The synthetic approach

(A= -NHC6H4SO3H). Exhaustion of those dyes is simple, cost-effective, and introduced a high on cotton fibers was very good and their washing quality product. fastness was excellent [84].

H2N NHCONH NH2 66 Fig. 10. Chemical structure of the compound 66.

The direct dye 67 (Fig. 11) can be produced Dyes 69 (Fig. 12) were useful for dyeing wool via diazotization followed by azo-coupling with and other protein fibers to afford a strong yellow 2,5-dichloro-4-(4,5-dihydro-3-methyl-5-oxo-1H- shade. Those dyes were prepared by coupling pyrazol-1-y1)benzene sulfonic acid and J-acid to the diazonium salt of aminophthalic acid with afford 67 with fair to good colorfastness properties 1-(4-sulfophenyl-3-methyl-5-pyrazolone) in an on cotton fibers. The colorfastness to light was aqueous medium containing sodium carbonate [87]. monitored to be the best property [85]. Reactive dyes 70 (Fig. 13) used for dyeing Monoazo dyes 68 (Fig. 12) were employed cotton fibers in yellow shades. The reactive dyes for dyeing polyester. They were synthesized by 70 were prepared via reaction of cyanuric chloride diazotization of 4-(2-phenoxyethoxycarbonyl) with p-CH3NHC6H4SO2CH2OSO3H and then aniline and coupling with 1-phenyl-3- with 1-(4-aminophenyl)-3-methyl-5-pyrazolone allyloxycarbonyl-5-pyrazolone. They exhibit which was coupled with the diazonium salt of yellow shade on polyester [86]. 2-aminophthalene-1,5-disulfonic acid [1, 2].

OH CH 3 Cl H2N N N N N N NHCONH N SO3Na O SO3Na 67 Cl Fig. 11. Chemical structure of the direct dye 67.

Egypt.J.Chem. 61, No.5 (2018) 911 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

R2 CO2H OH XO2C N N CO2R N N N SO3H HO N N N R3 R1 68 Ph CO2H 69 X= phenoxyethyl, benzyl R1= CH3, HC; =O R= alkenyl R2, R3= H, Cl Fig. 12. Chemical structure of monoazo dyes.

R= (un)substituted phenyl, naphthyl R5 R3 R6 R1= (un)substituted lower alkyl R R2= H, R3= H, CH3, RN N N N N 1 R4= CH3, CH3O2C N N N N R5= OH, NH2 R5 R 2 R7 R = Halogen 70 6 R7= SO2CH2=CH2 Fig. 13. Chemical structure of Reactive dyes 70.

Dyes 71 (Fig. 14) were prepared Reactive dyes 72 (Fig. 14) are beneficial by diazotization of p-carbotetrahydr of for the coloration of hydroxyl and carbonamide urfuryloxyaniline and azo-coupling with group containing fabrics. A sodium salt neutral 1-phenyl-3-carbo-(n-hexyloxyl) pyrazolone. solution of 4-(β-sulfatoethylsulfonyl)aniline They possess good dyeing power and was subjected to diazotization process and the produced diazonium salt was cyclocondensed colorfastness in dyeing hydrophobic fibers in and coupled with diethyl acetyl succinate. They yellow shades, particularly polyester [1, 2]. have been applied in the coloration of cellulose- containing fabrics in yellow shades [88].

R1 OH R3 R1 SO2Y XO S D N N N RO2C N N CO2R3 2 R R2 N 4 R R 2 HO N N D= benzene ring residue or C6H4NHCOC6H4 71 Ph R= CO2H; R1, R3= H, CH3, OCH3, Cl, Br R= alkyl, alkenyl R2, R4= H, CH3, CH2CH3 R1, R2= H, Cl, Br X, Y= thiosulphatoethyl, vinyl 72 R3= C5-8-alkyl, aryl NaO2C N N N N OH SO2R

73 R= CH3

SO3Na

Fig. 14. Chemical structure of Reactive dyes. Egypt.J.Chem. 61, No. 5 (2018) 912 TAWFIK A. KHATTAB AND MOHAMED REHAN

Water-soluble pyrazolone dyes 73 (Fig. 14) Naphthylazo reactive dye 75 is useful for were prepared by coupling the diazonium salt of dyeing fabrics containing hydroxyl or carbonamide 3-aminophenylmethylsulfone with 3-carboxy-1- group. It was prepared via diazotization of (4-sulfophenyl)-5-pyrazolone and hydrolysis in 4-(β-sulfatoethylsulfonyl) aniline followed by an alkaline environment. They dyed polyamide cyclization with acetyl succinic acid diethyl ester and wool fibers in yellow to red shades with at pH= 4. The produced pyrazolone intermediate satisfactory colorfastness to light, washing, was azo-coupled with 6-(β-sulfatoethylsulfonyl)- rubbing and perspiration [89]. 1-sulfo-2-naphthylamine diazonium salt to give the reactive dye 75 (Fig. 16) which was employed Reactive chloro or fluorotriazines of disazo on cellulosic fiber in a fast yellow shade [91]. reactive dyestuffs 74 are practical in combination with disperse dyestuffs on textile fibers containing A benzotrizole group was incorporated in the -OH or -NHCO- group particularly cellulose/ chemical structure of the reactive azo dye 76 (Fig. polyester blend affording greenish-yellow shades. 16) which is useful for dyeing wool, polyamide, Such disazo reactive dyestuffs 74 were synthesized or cellulosic fabrics in a fast yellow shade. It via condensation of cyanuric chloride with was prepared via azo-coupling of 2-amino- 4,4´-diamino-2,2´-stilbenedisulfonic and then 4-[2-(β-hydroxyethylsulfonyl) phenylamino] with 4-sulfo-m-phenylenediamine, diazotization benzenesulfonic acid diazonium salt with the product and finally coupling with 3-methyl-1- 3-methyl-1-( β- hydroxyethylsulfonylphenyl)-5- [4-(2-sulfatoethyl)sulfonyl]phenyl-5-pyrazolone pyrazolone [87]. [90] (Fig.15).

Cl HO3S OH N N HC NH NH N N N N N SO3H CH3 Cl SO2CH2CH2OSO3H OH N N H HC N NH N N 74 N N N SO H HO3S 3 CH3 SO2CH2CH2OSO3H Fig. 15. Chemical structure of disazo reactive dyes.

OH SO H 3 SO CH CH OSO H N N N 2 2 2 3 N 75 EtO2C HO3SH2CH2CO2S OH SO CH CH OSO H N N N 2 2 2 3 N N CH 76 N N SO3H 3 Fig. 16. Chemical structure of naphthylazo reactive dyes. Egypt.J.Chem. 61, No.5 (2018) 913 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

Cationic dyes 77 (Fig.17) have been useful Dyes 78 (Fig. 18) possess a high color yield and for dyeing acrylic, acid-modified polyamide, and are practical for dyeing textile fibers containing acid-modified polyester. The cationic dyestuffs hydroxyl group. Those dyes are synthesized by 77 were synthesized by diazotization of 5-amino- diazotization of 4-(2-sulfatoethylsulfonyl)-3- 3-methyl-1-phenylpyrazole and coupling with (2-sulfatoethylsulfonylmethyl) aniline and azo- N,N-dipropylaniline followed by alkylation with coupling with 1-(4-sulfophenyl)-3-carboxy-5-

(CH3)2SO4 [92]. pyrazolone [87].

H3C + R N 2 R1 N N N R1= CH3, CH2CH3, CH2CH2OH R3 R2= C3-6-alkyl; R1= C3-6-alkyl, (R4)n 77 A= anion; R4= H, Cl, CH3 Fig. 17. Chemical structure of Cationic dyes.

CO2H HO SOH CH CO S N N 3 2 2 2 N HO SOH CH CO S N SO3H 3 2 2 2 HO 78

R2 NC N R N N N 79 N NC R1 CH2CN R3 R, R1= H, alkyl; R2= Cl, Br; R3= OH, Cl

Fig. 18. Chemical structure of Cationic dyes.

Red and bluish-red dyes 79 (Fig. 18) were The triazole 81 was obtained by reaction of 80 synthesized via reacting [(4,5-dicyanoimidazole- with hydrazine in presence of mercaptoethanol and 2-yl)azo] anilines with haloacetonitriles or hydrazine dihydrochloride at 100°C for 4-5 hours. cyanomethyl benzene sulfonates and employed Only 80 with substituents R1= R2= Cl, when for dyeing polyester fibers [93]. subjected to same reaction condition, tetrazine 83 was obtained. Compound 81 (R = R = Cl) was Heterocyclic dyes containing 5-membered ring 1 2 with three nitrogen heteroatoms obtained using large amount of acetic acid and Friedman and Shechter described the direct heating for 40 hours. Dihydrotetrazine 82 was cyanation of aromatic halides which can be formed at first stage and rearranged to 81 under performed easily employing slight excess of acidic conditions or alternatively air-oxidized, in cuprous cyanide in dimethylformamide. A mixture presence of sodium nitrite, to the corresponding of haloaniline and excess of cuprous cyanide was tetrazine 83 (Scheme 17). Tetrazotization of refluxed for 5 hours in dimethylformamide and 81 (Scheme 17) was accomplished by adding then treated with ethylene diamine to produce 80 acetic acid as a co-solvent, and then coupled with 1 2 acetacetanilide to give yellow pigments 84. (R , R = H, Cl, CH3) (Scheme 16). Egypt.J.Chem. 61, No. 5 (2018) 914 TAWFIK A. KHATTAB AND MOHAMED REHAN

R1 R1 DMF H N X + CuCN H N CN 2 reflux 2 80 R2 R2 R R1 R1 1 N N HSCH CH OH 2 2 NH H2N CN + NH2NH2.H2O H2N 2 H+ N NH R2 R 2 R2 80 2 81 Scheme 16.

R1 R1 R1 N N NH2NH2 H2N CN H2N NH2 HN NH R2 80 R2 82 R2 oxidation rearrangement

R1 R1 R1 R1 N N N N H2N NH2 H2N NH2 N N N R R2 NH R 2 83 R2 81 2 2 Scheme 17.

The tetra-substituted pigments 84 (R1= R2= Cl resulted in ratings of 4 to 4-5. Compounds and CH3) were thermally less stable than others 85 (X=A= H; B= H, CN) were used to afford derivatives. The compound 84 (R1= R2= H) was metal complexes for application on wool and thermally stable till 316ºC and 84 (R1= H and nylon fibers. R2= Cl) stable at 320ºC which are considerably superior to Benzidine Yellow 7 (m.p. 200°C) [94] N-benzylated-1,2,3-triazolyl derivatives (Scheme 18). have been claimed as bright red dyestuffs of good colorfastness, and recently, analogous of 1,2,4-Triazole dyestuffs of the general 1, 2, 4-triazole dyes have been patented [1]. chemical structure 85 have been applied to hydrophobic fibers. The compounds 85 (X=H) The triazole azo dyes 86 (Fig. 19) were and their 5-methylthio analogues 85 (X=SCH ) synthesized by benzylation of azo dyestuff 3 which based on PhEtNCH CH NPhEt as azo- (Fig. 19) were found to be inappropriate for 2 2 polyester fibers in respect to substantivity and coupling moiety and 3-aminotriazole as diazo colorfastness properties. However, raising the moiety. Those dyestuffs may be employed dyestuff hydrophobicity by substitution at the for bluish-red coloration of acrylic showing 5-position with (nitro) phenyl group enhanced rapid and complete dye uptake from the dye- the dyeing features. The light fastness bath with good colorfastness. To obtain 87 evaluation was generally poor on polyester, (Fig. 19), benzylation occurs with benzyl- cellulose triacetate and nylon fibers unless p-toluenesulfonate in dimethylformamide a bis-cyano substitution was used which containing zinc oxide at 90°C [87]. Egypt.J.Chem. 61, No.5 (2018) 915 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

R1 R1 R1 R1 N N N N NaNO2 + + H2N NH2 N2 N2 N H+ N R2 NH R R2 H 81 2 2 R2

R1 R1 O N N O O O N N N N O N O N H - NH R2 H R2 HN

Scheme 18

X N N C2H4A HN N N N 85 C2H4B +2 R2 R N N 2 Et Et N N -2 R1 N N N NCH2CH2N N N R A N 1 R2 86 R2

R1= H, CH2Ph; R2= benzyl, p-methyl benzyl, n-methoxy benzyl; A= Cl CH N 3 N + -2 + N N N CH3 SO4 CH3 N CH3 CH 3 87 Fig.19. Chemical structure of 1, 2, 4-Triazole dyes.

Dyes 87 were beneficial for dyeing textile methylene group toward pyridone condensation. substrates and synthesized by azo-coupling Compound 89 (Fig. 20) is a very greenish-yellow 3-amino-1,2,4-triazole diazonium salt with disperses dye while 90 (Fig. 20) is a greenish- N-benzyl-N-methylaniline. The product was yellow cellulose reactive dyestuff. Compound dispersed in a mixture of water and magnesium 91 (Fig. 20), a cationic dyestuff for acrylic fibers, oxide and alkylated with (CH3)2SO4. Acetic was synthesized from pyridinium substituted acid was added, the mixture heated and 25% pyridone. In compound 90, the pyridone fragment ammonium hydroxide solution was added to the is substituted by sulfomethylene group which mixture then stirred and filtered to provide highly introduced by Hegar. Generally, dyestuffs have concentrated dyestuff solution [95]. very good colorfastness and coloration properties and can replace more costly styryl dyestuffs Heterocyclic dyes containing 6-membered ring on polyester fibers for very greenish-yellow with one nitrogen heteroatom shades and high tinctorial strength. They are less Pyridine 88 (X is a pyridinium group) (Fig. successful on wool and polyamide fibers due to 20) can be synthsized from pyridinium acetamide. their low light fastness on these fibers. The pyridinium group activates the adjacent Egypt.J.Chem. 61, No. 5 (2018) 916 TAWFIK A. KHATTAB AND MOHAMED REHAN

A CH3 CN X N N O NH HO N O HO O O CH3 88 B S N 89 O CH3 Cl H N N N SO3H HO C2H5 N N HO3S HN 90 N N O

CH3 H2C SO3H

CH3 N - + X N N N N O NH 91 HO Fig. 20. Chemical structure of Pyridine dyes.

CH3 CH3 CONH CH3 CONH2 HO3S CH2 2 + HO3S CH2 CONH2 H [D-N2] CH2O + NaHSO3 N N D O N O O N O O N O C2H5 C2H5 CH C2H5 H2 3 HO S C N N D - 3 OH - + [NCO] HO N O aniline C2H5 90 NHCONH2

CH3 CH3 CH3 CN CN CN POCl3 RNH2 80-120°C HO N O Cl N Cl R N N N R H H H 92 93 Scheme 19.

Egypt.J.Chem. 61, No.5 (2018) 917 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

Cyanomethylpyridone was reacted with an evident hypsochromic nature, since with phosphorus oxychloride to form 92 followed by highly bathochromic 2-cyano-4-nitroaniline reaction with amines to give 93 (Scheme 19) diazo, neutral red is produced. Compound 96 which was proposed for the synthesis of dyes 94- is recognized acid dye for polyamide fibers. 96 (Fig. 21). Compounds 94 and 95 are dispersing Compound 98 was prepared using malononitrile dyes for polyester fibers with extremely brilliant dimer as starting material. shades and good light fastness. Dye 95 exhibits Adding hydrobromic acid to nitrile group,

CH3 CN

94 O2N N N NH (CH2)3 O (CH2)2 O N H2N

CN CH3 CN

95 O2N N N N (CH2)3 O (CH2)2 O N H HOH2CH2CH2N

Cl CH3 CN H 96 HO3S N N N CH2 CH2 OH N Cl HO(H2C)2H2N

Fig. 21. Chemical structure of dispersing dyes.

NH2 N NH NH2 CN CN CN CN + CH2 THF CH2 CN HBr CN CN CN CN N N HN Br

NH2 NH2 NH2 CN CN CN R1 X= -NH2, -NHR, -N R -OR, -SR 2 HN N Br H2N N Br H2N N X 97 Scheme 20.

Egypt.J.Chem. 61, No. 5 (2018) 918 TAWFIK A. KHATTAB AND MOHAMED REHAN followed by Thorpe-Ziegler ring-closure and In general, dyes 103-105 displayed poor light formation of isomeric mixture of 97 (Scheme fastness on polyester substrates [96]. 20). Bromine can be exchanged by nucleophilic reaction with amines, phenols, alcohols or Compound 106 was fused with 107 for 2 hours mercapto compounds to afford 98. Red dye 99 at 200ºC, to give 108 which was esterified by reflux for 8 hours with ethyl alcohol in presence of H SO was prepared from 98 for polyester revealing 2 4 very good light fastness and high brilliancy. to obtain 109. Both compounds 108 and 109 was Triaminocyanopyridine dyes 100 (Scheme 21) coupled with 4-substituted-benzenediazonium chloride (R= H, Cl, CH , OCH ) to give dyes 110 were synthesized using malononitrile dimer 3 3 followed by azo-coupling with diazo material and 111, respectively (Scheme 22). Mixture of to offer hydrazone which was then reacted with 108 and 112 was heated in phosphoric acid for 2 amine, alcohol or mercapto material to result in hours at 170-180ºC, to give 113 which were also ring-closure forming cyanopyridine, whereby two obtained by similar reaction between 109 and 112. isomers may arise. When employing methanol The produced compound 113 was coupled with 4-substituted-benzenediazonium chloride to provide (Y= -OCH3), for example, in ring-closure step, a yellow dyes 101 (Scheme 21) with high standard yellow dyes 114. Compound 112 was condensed of colorfastness, was formed [68]. with p-aminobenzoic acid in polyphosphoric acid, to obtain 115, which upon fusion with 116 at 210- Condensation of isatin with 102 in presence 220ºC for 4 hours, gave 116 which was coupled with of phosphorus oxychloride in refluxing benzene 4-substituted-benzenediazonium chloride to give for 5 hours, yielded disperse dyes 103-105 117 (Scheme 23). (Scheme 21) with violet shade. The sublimation Compounds 110 and 111 were applied on fastness of dye 103 was evaluated between 2-3.

NH 2 NO 2 H2N CN N O2N N N N H H2N N N H 99 98 H2N CN

NH NH NH2 2 2 H + NC N N D NC NC N N D Y-H CH2 + D N2 CN CN CN CN H2N N Y 100 CH3 NH2 CN O CH NC N N 3 CN HO N O N MeO N NH 2 R' 103 H O N O 101 102 R'= CH ,o-Tolyl 3 R' O O H CH3 O CN R' N N N H O N O CH O 105 3 104 R' CN Scheme 21. Egypt.J.Chem. 61, No.5 (2018) 919 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

O O

MeO O + NH2CH2COOH MeO N CH2 COOH 107 108 O 106 O + - C H OH/H SO ArN2Cl 2 5 2 4

O O

MeO N CH COOH 2 MeO N CH2 COOC2H5

N O O 109 N H + - ArN2Cl O

MeO N CH2 COOC2H5 R 110 N O N H 111

Scheme 22.

polyamide and polyester fibers to afford yellow CH3, NO2) (Scheme 24). shades. The carboxylic acid group in 110 made them more suitable than 111 for polyamide fibers, The fabrics dyed with some derivatives of although 111 afforded more intense dyeing on 122, where R= X= H, displayed greener shade polyester fibers. Dyestuffs 114 and 117 also and shorter radial chroma than those derivatives, where X= NO or R= N,N-dimethylethylene. For afforded yellow shades. The existence of a bulky 2 dyes, where X, R= CH , shades were yellower phenyl bridge in 117 among benzimidazole 3 and pyridone rings resulted in much weaker and displayed longer radial chroma. They were dyeing than the alkylene bridged dyestuffs 114. appropriate for dyeing polyester substrates and Overall light fastness of dyestuffs was good gave yellow or greenish-yellow shades [98, 99]. and sublimation fastness of all dyestuffs was o-Hydroxyanilines were diazotized and coupled excellent. Washing fastness for 111, 114 and 117 at pH 3-4, with pyridones dissolved in sodium (Scheme 23) was better than that of 110 [97] carbonate solution, to produce intermediates (Scheme 22). 123. Purple azo pyridone chromium complexes 124 were prepared by refluxing a mixture of The 2-pyridone compound 120 was sodium acetate, ammonium chromium(III) prepared from mixture of ethylcyanoacetate sulfate and 123 for 2-3 hours in formamide 118, ethylacetoacetate 119, and amine in an (Scheme 25). ethyl alcohol under reflux and in presence of piperidine as a catalyst. The aniline derivatives The azopyridone 123 were applied on 121 were diazotized and their diazonium salts polyester to display good washing fastness, but were coupled with the 2-pyridone 120 at pH very poor light fastness, while the complex dye 3-4 to give pyridone dyes 122 (R= H, CH , 124 displayed excellent washing and light fastness 3 on wool fibers [100]. CH2CH2OH, CH2CH2N (CH3)2, C12H25; X= H,

Egypt.J.Chem. 61, No. 5 (2018) 920 TAWFIK A. KHATTAB AND MOHAMED REHAN

O NH2 N H3PO4 H2 108 + MeO N C NH2 N H 112 O 113

H3PO4 + - ArN2Cl

O 109 + 112 H2 N MeO N C N H N O N H 114

R N H N 112 + H2N COOH 2 N 115 H O N 106 + 115 MeO N N H O + - 116 ArN2Cl O N MeO N N N O H N H 117

R Scheme 23.

Egypt.J.Chem. 61, No.5 (2018) 921 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

CH3 CN Ethanol CNCH2COOC2H5 + CH COCH COOC H + R-NH 3 2 2 5 2 reflux 120 118 119 HO N O R CH3 HCl/NaNO2 + - 0-5°C CN X NH2 X N NCl X N N 0-5°C 120 121 HO N O 122 R Scheme 24. R 2 CH3 R CN 2 CH3 N N CN N N O O N O Cr R1 R1 HO N O O O OH O N R 123 1 N N R1= H, n-Bu, iso-Bu NC R2= H, CH3, Cl, NO2 CH R 3 124 2 Scheme 25.

The m-nitrobenzene sulfonic acid 125 was to afford 127. This was followed by reduction of 127 converted to its benzenesulfonyl chloride form 126 using tin(II) chloride and concentrated hydrochloric [101] which was then interacted with substituted acid afforded 128. Diazotization of 128 followed by phenols at room temperature and under alkaline azo-coupling with substituted pyridones afforded environment in a biphase system employing tetra-n- dyestuffs 129 (R1= H, p-Cl, m-CH3, o-CH3; R2= butylammonium bromide as a phase transfer catalyst, CH3, C2H5, C6H5) (Scheme 26).

O2N O N O2N R1 2 HO O

SO3H SO2Cl S O O 125 126 127

CH3 CN H2N R1 O N O S O R1 N N O H O O R2 O S 128 O 129 Scheme 26. Egypt.J.Chem. 61, No. 5 (2018) 922 TAWFIK A. KHATTAB AND MOHAMED REHAN

Reaction of m-hydroxyaniline 130 with CH3, C2H5). Lighter dyeings were obtained from substituted benzenesulfonyl chloride in presence N-phenylpyridones which displayed moderate of tetrabutylammonium chloride as PTC light fastness. Sublimation fastness was evaluated afforded 131. Dyes 132 (R1= H, m-CH3; R2= between good to very good for all dyes [102].

CH3, C2H5, C6H5) was synthesized from 131 via usual diazotization and azo-coupling reactions The azo dyes 133 (Fig. 22) were prepared by (Scheme 27). diazotization of heterocyclic amine and coupling to the appropriate coupling component [103]. The hydrazone compound 129 dyed polyester in bright greenish yellow shades showing excellent Dyes 133 used as disperse dyes giving good deep shades, particularly the derivatives of 129 dyeing on hydrophobic fibers such as polyester, (where R = H; R = CH , C H or R = o-CH ; R = polyamide and cellulose acetate fibers. Acceptable 1 2 3 2 5 1 3 2 exhaustion, color uniformity and color yield CH3, C2H5). In all cases, dyes 129 offer better shades than that of 132 which include Samaron were achieved. The colorfastness to solvent, wet treatment and rubbing was preferred on polyester, Yellow 6 GRL 132 (R1= H; R2= C2H5), making them highly competitive commercially. Light whereas the light fastness was at its highest on fastness of majority of dyes was good, particularly cellulose acetate [104].

129 (R1= H; R2= CH3, C2H5 or R1= o-CH3; R2= PMAN, 1-((pyridin-2-yl)methyleneamino)

H2N H2N R1 SO2Cl O OH O S O 130 131

CH3 CN

N O R 1 N N O H O R S O 2 132 O Scheme 27.

X2 N N N N X3 X1 133

X1= H, CH3, NHCOCH3; X2= CH3, CH2CH3, CH2CH2OH, CH2CH2CN, CH2CH2OCOCH3; X3= CH3, CH2CH3, H, CH2CH2OH, CH2CH2CN, CH2CH2OCOCH3 Fig. 22. Chemical structure of the azo dyes 133.

Egypt.J.Chem. 61, No.5 (2018) 923 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ... naphthalen-2-ol, was prepared via reaction of of wool to these metal complex dyestuffs is 2-pyridinecarboxaldehyde with 1-amino-2- satisfactory [105]. naphthol hydrochloride in ethanol as a solvent Dissolving PMAP, 2-(pyridin-2-yl) and in presence of CH3COONa.3H2O. The salt Cu (CH COO) H O was dissolved in methanol methyleneamino)phenol, in methanol and adding, 3 2 2 with stirring, a solution of CrCl .6H O in methanol and mixed with solution of PMAN in ethanol. The 3 2 produced mixture was refluxed for 30 minutes and followed by reflux for 2 hours and then allowed to stand overnight at ambient conditions. The dye a saturated solution of NaClO4 was then added to afford 134. PMAN was dissolved in methanol, and 137 (Scheme 28) was obtained upon the addition of a saturated solution of NaClO4. a solution of Ni (CH3COO)2 4H2O in methanol was then added with stirring. The produced mixture Cr(III)-PMAP complex is a good dyestuff was stirred for 5 hours at ambient temperature and for wool and related fibers showing a higher then left to stand overnight, to yield 135 (Scheme exhaustion of dye at higher pH value and

28). PMAN and Co(CH3COO)2.4H2O was mixed introduced a very good washing fastness [106]. in methanol followed by stirring for 6 hours at room temperature, and a saturated methanolic Disperse dyes 138 (Fig. 23) were utilized for coloring cellulose acetate and nylon fibers. They solution of NaClO4 was then added, to give 136 (Scheme 28). can also be applied on silk to afford deep yellow shades. A very low dye exhaustion was monitored for Both wet and light fastness properties are Ni (PMAN)2 complex, while a higher exhaustion and better color depth was monitored for better than those of acid dyestuffs of same molecular weight, and generally they displayed Co(PMAN)2 complex. Highest K/S was obtained for Cu-PMAN complex. High washing fastness good colorfastness [107]. was obtained, confirming that the substantivity

N N CH O CH N - N H2O Cu ClO4 Ni N O CH N O

135 134 + +

N N O CH O CH N - - Co N ClO4 2H2O N Cr N ClO4 CH N O CH N O

136 137

Scheme 28.

Egypt.J.Chem. 61, No. 5 (2018) 924 TAWFIK A. KHATTAB AND MOHAMED REHAN

H CH2CH2X Ar N N N N N CH2CH2X R O Ni O . H O 138 N 2 N X= OH, CN Ar= R= H, CH3 H N 139 Fig. 23. Chemical structure of the Disperse dyes 138 and the dye complex 139.

PMAP was prepared from 2- The complex dye Cu-PMAP can be applied pyridinecarbaldehyde and 2-hydroxyaniline [108, on wool at pH value higher than the fiber 109]. The dye complex 139 (Fig. 23) was prepared isoelectric point because at pH 4.5, the shade by addition of PMAP to stirred methanolic became more yellower than at pH 5.5. Also, solution of Ni (II) acetate tetrahydrate. the exhaustion was monitored to increase more quickly at pH 5.5 than at pH 4.5. Wool showed Ni-PMAP was satisfactory dyed polyamide very good washing fastness [113]. fibers. High washing fastness was monitored for Ni-PMAP at 95°C. Results indicated that Ni- Pyridone disperse dyestuffs 148 are practical PMAP is a satisfactory metal complex dye for for dyeing synthetic fibers and can be synthesized polyamide and wool fibers [110]. via azo-coupling of the diazonium salt of 4-(R CO)-C H NH with hydroxypyridone 147 Rieche et al. [111] described introducing an 1 6 4 2 aldehyde group employing dichloromethylalkyl [2] (Scheme 30). ethers in combination with Friedel-Crafts catalyst Different derivatives of disazo dyes 149 were and in dichloromethane as a solvent. The interaction applied on polyester to afford orange shade with of pyrene 140 with dichloro(methoxy)methane 141 excellent build up and alkali fastness. They were in presence of aluminium chloride afforded the prepared via azo-coupling of 4-aminoazobenzene precursor 142, which was then hydrolyzed to offer diazonium salt with either 1-ethyl-3-cyano-4- 143. Compound 144 was prepared by condensation methyl-6-hydroxy-2-pyridone or 1-(ethylhexyl)- of 143 with ethyl cyanoacetate. The cyclization of 3-cyano-4-methyl-6-hydrxypyridone [114] the pyrene derivative 144 with ketones (R= pheny, (Scheme 30). l, 2-naphthyl, 2-fluorenyl, 2-pyrenyl, 2-pyridyl), produced 145 in presence of excess amount of Azopyridine dyes 150 were produced ammonium acetate (Scheme 29). from the coupling of 2-chloro-4-nitroaniline The pyrene derivative dye 145 containing diazonium salt with 2-aniline-3-cyano-6-(γ- 2-pyridyl group (R) in its molecular structure, methoxypropylamino)-4-methyl-pyridine. Dye displayed greener hue and shorter radial chroma 150 dyed polyester with a bluish-red shade than for the dye derivative with phenyl group showing a light fastness value at 6 [115]. (R). Dyes with R= naphthyl, fluorenyl or pyrenyl The azopyridone dye 151 is practical at group at the 6-position of the pyridone ring possess yellow shade, high color purity, and are appropriate high temperature with excellent colorfastness as disperse dyestuffs for polyester fibers [112]. on polyester affording greenish-yellow shade of superior abrasion resistance. Dye 151 was Azomethine dye 146 (Scheme 30) was prepared by coupling the diazonium salt of synthesized by mixing Cu(CH3COO)2.H2O and n-pentyl-4-amino-3-nitrobezoate with 3-cyano- PMAP in methyl alcohol for 6 hours at ambient 1,4-dimethyl-6-hydroxy-2-pyridone [116] temperature, and then left to stand overnight (Scheme 30). followed by the addition of saturated methanolic solution of NaC1O4.H2O. Egypt.J.Chem. 61, No.5 (2018) 925 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

Cl OMe CHO

AlCl3 H2O + Cl2CHOCH3 141

143 140 142

CN COOC2H5 O

COOC2H5 R CH3 Piperidine CN

145 R N O 144 H Scheme 29.

O Cu N - N ClO4 N Cu O O O

CH3 146

R4 O R R2 4 R1 N N R2 HO N O HO N O R3 147 148 R3 R1= C1-5 alkyl; R2, R3= (un)substituted C1-12 alkyl, R4= H, C1-4 alkyl

CH3 Cl CH3 CN N N N N CN

O2N N N NH 149 HO N O N H3CO(H2C)2HN 150 R= CH2CH3, R= CH3, C3-8 alkyl R

NO2 NO 2 CH3 CH3 R1O N N CN H3C(H2C)4O2C N N CN HO N O 151 HO N O 152 R2 CH 3 R1= C1-4 alkyl; R2= iso-pr, Bu

Scheme 30. Egypt.J.Chem. 61, No. 5 (2018) 926 TAWFIK A. KHATTAB AND MOHAMED REHAN

Pyridone azo dyes 152 of different derivatives reaction mixture, acetic acid was added and were obtained by coupling alkoxynitroaniline the resulting intermediate was coupled with diazonium salt with different derivatives of 4-nitroaniline diazonium salt to produce 153 2-pyridone as coupling components. The produced [118]. dyes are useful for dyeing polyester substrates in fast shades [117] (Scheme 30). Dyes 154 (Scheme 31) were synthesized by reacting 2,6-dichloro-3-cyano-4-methyl-pyridine Pyridyl azo dyes 153 utilized for wool, with 4-amino-2,2,6,6-tetraethyl piperidines in dry polyamide and acrylic fibers in a fast red shades, CH3OH with stirring at 40-50°C. The mixture was are synthesized by reaction of 2,6-dichloro- then poured into water, the produced precipitate 3-cyano-4-methylpyridine with sulfanilamide was then condensed with ethanolamine, and finally at 135-140°C to form N-(6-chloro-3-cyano- the product was azo-coupled with the diazonium 4-methyl-2-pyridyl)sulfanilamide which was salt of 2-amino-5-chlorobenzophenone. The dissolved in N-methyl-2-pyrrolidone and refluxed colorant 154 dyed acrylic fibers in fast yellow with 2-hydroxypropylamine. After cooling the shade [1, 2].

CH3 CH3 A N N CN A N N CN 153 CH3 HOH2CH2CHN N N CH3 H RHN N N SO2NH2 NH.HCl H 154 A= 4-nitrophenyl, 2-benzoyl-4-chlorophenyl CH3 CH3 R= cyclohexyl, 2,2,6,6-tetraethyl piperidyl, A= aryl, 2,4-Cl (Ph) C6H3 2-hydroxy propyl

CH3 NO2 A N N CN CH3 CH N N R 3 CH3 1 N N CH3 H3C H R HN NH.HCl HO N O 156 155 R2 CH3 CH3 CH CH 3 3 R= Cl, R1= CN A= aromatic heterocyclic ring R2= C3H6OC2H4OPh

R CH3 CH3 R1 N N CN Ar N N CN CH3 R2 N N NHCH2CH2OH HO N O H3C H 157 (CH ) O ZR HN .HCl 2 n 2 3 158 CH3 CH3 R= 2-CH3; R1= 4-NO2; R2= H R3= Ph; Z= CH2, C2H4, C2H4O; n= 2, 3 Ar= aromatic heterocyclic ring Scheme 31. Egypt.J.Chem. 61, No.5 (2018) 927 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

Reaction of 2, 6-dichloro-3-cyano- Diazotization of 2,4-CH3(NO2)C6H3NH2 and 4-methylpyridine, 4-amino-2, 2, 6, azo-coupling with 3-cyano-6-hydroxy-4-methyl- 6-tetraethylpiperidine and N-methyl-2- 1-[3-(2-phenoxyethoxy)propyl]-2-pyridone pyrrolidone under heating at 145-155°C, followed afforded pyridinone dyestuff 157 (Scheme 31) by cooling, and finally azo-coupling with 2-cyano- which used on polyester [2]. 4-nitroaniline diazonium salt, afforded dyes 155 which dyed acrylic fibers in fast red shade [1, 2]. Dyes 158 were derived from 2,6-diaminopyridine via reaction of 6-chloro-3-cyano-2-[(2-

Diazotization of 2,5-Cl(NO2)C6H3NH2 and hydroxyethyl)amino]-4-methylpyridine with azo-coupling with 3-cyano-6-hydroxyl-1-(β- 4-amino-2,2,6,6-tetramethylpiperidine followed by phenoxyethoxypropyl)-4-methyl-2-pyridone coupling the product with aromatic diazonium salt afforded 156 (Scheme 31) which was applied on (Scheme 31). They have been suitable for dyeing polyester [1, 2]. acrylic fabrics [2].

Q CH CN 3 COOH H R5 N N N N Q2 N N NH NH SO3H N N N Q1 NHR1OR2O N z O N OH H SO3H Cl N N 160 159 NR3R4 Q, Q = halogen, CN; Q = halogen, CF CH 1 2 3 CH3 3 R1, R2= ethylene, propylene; R3, R4= H, alkyl N XN N CONH2 H2NOC NX R5= H, halogen; Z= halogen 162 CH3 O N OH H HO N O Cl N N N N CH2SO3H N CH2-CH2(CH2)2CH2-CH2 SO3H X= sulfonated aromatic group of fiber-reactive N O Cl CN HO vinyl sulfone or halotriazine type from diazo 161 CH3 component. SO H CH3 3

N N X N NHZY O N OH HN R N N 163 Cl R= H, alkyl; X= H, CH3; Z= phenylene, naphthalene Y= SO2CH=CH2; R= alkali removable group Scheme 32.

Trifluorotriazine was reacted with 2-anilino- diazotizing the product, and then azo-coupling 3-cyano-4-methyl-6-[2-(2-hydroxyethoxy) with citrazinic acid (Scheme 32). Finally reacting ethylamino]pyridine, then reacted with the product with 4-H2NC6H4SO3H to afford yellow 3-ethoxypropylamine. The product was coupled shade on both of cotton and rayon fabrics [2]. with 2, 4-dichloroaniline diazonium salt to afford dye 159 (Scheme 32) which was applied on Reactive dye 161 (Scheme 32) was prepared polyester-cotton blend fabrics [2]. via reaction of 5-cyano-2, 4, 6-trichloropyrimidine with 2,4-diaminobenzene sulfonic acid. The Reactive dyestuff 160 for rayon and product was then diazotized and azo-coupled cotton fibers was synthesized by reacting with 1, 4-dimethyl-6-hydroxy-3-(sulfomethyl)-2-

2,4-(NH2)2C6H3SO3H with cyanuric chloride, pyridone to afford 161 for cotton fibers [119]. Egypt.J.Chem. 61, No. 5 (2018) 928 TAWFIK A. KHATTAB AND MOHAMED REHAN

Water soluble reactive pyridine disazo dyes Reactive dye 163 was synthesized and employed 162 were applied on hydroxyl or carbonamide for dyeing cotton fibers. Thus, 1,3-phenylenediamine- containing fibers. It was synthesized via 4,6-disulfonic acid was subjected to condensation cyclocondensation of N, N-bis (cyanoacetyl)- with cyanuric chloride. The 3-(2-sulfatoethylsulfonyl) 1,6-diaminohexane with ethyl acetate to give aniline was then diazotized and azo-coupled with hexamethylene dipyridine. The product was 1-ethyl-4-methyl-6-hydroxy-2-pyridone to afford then coupled with the diazonium salt of the dyestuff 163 [121] (Scheme 32). condensation product from cyanuric acid with 4-(2-sulfatoethylsulfonyl) aniline or Reaction of 164 with 2,6-difluoro-4-methyl-5- 1,3-diaminobenzene-4-sulfonic acid [120] chloropyridine afforded yellow reactive dyestuff (Scheme 32). 165 used for fibers containing OH groups such as cotton fibers [122] (Scheme 33).

CH3 CH3 H CN R R N N N 2

HO N O ZR3 HO N O 164 CH2CHBuEt 165 R1

R= H, NO2; R1= alkyl or aralkyl; Z= O or S; R2= CN R3= active haogen-containing 6-membered N-heterocyclic rings

SO3H SO3H CH3 CH 3 N N CH2SO3H N N X R2 N O N A Y HO N O N N O N OH CH CH NH N H N N 2 2 R1 N 166 N+ Cl 167 A= (un)substituted phenylene,naphthalene, - R1, R2= H, C1-4 alkyl; X= CH3, SO3H; Y= SO2CH=CH2, CO2 SO2CH2CH2Z; Z= leaving group HO R3 Cl N N CONH N N O Cl N SO H 168 3 R1 R2 R1= H, CO2H; R2= H, CH3; R3= H, C1-6 alkyl Scheme 33.

1, 3-(NH2)2C6H2(SO3H)2-4, 6-difluoro-5- Bifunctional reactive dyes 167 for dyeing -OH chlorotriazine was neutralized using sodium and –NHCO- containing fabrics were prepared hydroxide and followed by treating with cyanuric from condensation of 1-(2-aminoethyl)-4-hydroxy- chloride and the resulting product was then 4-methyl-3-(sulfomethyl)-2-pyridine with cyanuric condensed with m-H2NC6H4SO2CH2CH2OSO3H chloride. The product was then subjected to followed by diazotization and coupling with condensation with morpholine and nicotinic acid, 1-ethyl-6-hydroxy-4-methyl-2-pyridine to give and the resultant intermediate was azo-coupled with reactive dyes 166 for dyeing cotton fibers in the diazotized 2-amino-6-(2-sulfatoethylsulfonyl)- brilliant fast yellow shades [122]. 1-naphthalenesulfonic acid (Scheme 33).

Egypt.J.Chem. 61, No.5 (2018) 929 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

Compound 168 dyed cotton fabrics as reactive condensed with urea or guanidine derivatives to dye in strong greenish-yellow shades [123]. introduce the final brilliant disperse dyestuff 174 Reactive dye 168 was synthesized by diazotization (Scheme 34) of red shade and generally high of 4-acetamido-2-aminobenzenesulfonic acid and standard of colorfastness [68]. azo-coupling with 3-carbonoyl-6-hydroxy-1, 4-dimethyl-5-(sulfomethyl)-2-pyridone The acid dyes 175 (Scheme 35) and 180 (Scheme 33). The product was then subjected to (Scheme 36) were formed by azo-coupling the deacetylation followed by condensation with 2, sulfanilic acid diazonium salt 178 to ß-naphthol 3-dichloro-6-quinoxalinecarbonylchloride to offer and Schaeffer’s acid, respectively. Treatment 168 in greenish-yellow shade on cotton fibers [2]. of 175 and 180 with phosphoryl chloride in N, N-dimethylacetamide/acetonitrile/sulfolane Heterocyclic dyes containing 6-membered ring afforded 176 (Scheme 35) and 181 (Scheme 36). with two nitrogen heteroatom Condensation of N-methylpiperazine with 176 Reaction of 169 with substituted amines is and 181 in acetone at 35-50°C for 2 hours and in the simplest way to produce aminopyrimidine presence of K2CO3 as a base, afforded disperse 170. In disperse dye chemistry, the pyrimidine dyes 177 (Scheme 35) and 182 (Scheme 36) which couplers are hypsochromic compared to the was then treated with excess of methyl iodide in dialkylaminobenzene couplers, particularly boiling acetone to give cationic dyes 178 (Scheme for the case of red dye 172 which contains a 35) and 183 (Scheme 36). highly bathochromic dinitro-chloroaniline- diazo component. Brilliant red dyes 171-173 The dye 177 did not possess good sublimation (Scheme 34) possess a high light fastness and fastness, while 182 introduced a very high high molar extinction coefficient when used as sublimation fastness. Light fastness of 178 and 183 disperse dyestuffs for polyester fibers or as acid on acrylic fibers displayed significantly better values dyestuffs for polyamide fibers. than that observed on cationic dyeable polyester, and it is quite good in cases involving 178. Disperse and However, dyestuffs for cellulose fibers from cationic dyestuffs derived from C.I. Acid Orange 7 such components are of no significance, due and 176 gave much deeper shades, higher exhaustion to their unsatisfactory light fastness. The diazo and higher light fastness than the dyes prepared from component was coupled with malondialdehyde intermediate 181 [124] (Scheme 36). to result in azo compound, which was then

H H O O Cl Cl R N N R POCl3 R-NH2 HN NH N N N N 169 170 O Cl HN R

Cl HN NO2 HN N H N H O2N N N N C2H5 O2N N N N C2H5 N N HN Cl HN 171 CH2 CH2 OH CH CH OH 172 2 2

NO2 H2N N O2N N N N H N 173 H2N CN H O H2N N N N + R N N R O HN N H R= -NH2, -NH-R1; -O-R1, -S-R1 174 Scheme 34. Egypt.J.Chem. 61, No. 5 (2018) 930 TAWFIK A. KHATTAB AND MOHAMED REHAN

N N SO Na N N SO Cl 3 POCl3 2 DMA/CH CN/sulfolane OH 3 OH 55-60°C,1h 175 176

Acid Orange 7 Amine/K2CO3 acetone, 35-50°C

N N SO2R1 N N SO2R1 OH CH3I,acetone OH 178 reflux for 2h 177 R = 1 + - R1= N N (CH3)2I N N CH3

Scheme 35.

OH N N SO3Na

+ - NaO3S NaO S N NCl OH 3 pH= 9, 0-5°C, 5h 180 NaO S 179 3 2 POCl3.DMA/CH3CN/sulfolane 55-60°C,1.5h

N N SO2R1 N N SO2Cl OH Amine/K2CO3 OH acetone,35-50°C R1O2S 181 182 ClO2S R1= N N CH3

CH3I, acetone N N SO2R1 reflux, 2h OH 183 R1O2S R1= + - N N (CH3)2I

Scheme 36.

Egypt.J.Chem. 61, No.5 (2018) 931 A REVIEW ON SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC ...

(SO3H)0-1 OH O RO N N NH N H HO3SO(H2C)2O2S N N O N N R1 N HO3S 185 O CH2CH2SO3H 184 Cl F R1= halogen; R= cyclohexyl, aryl

(SO3H)m R OH 1 F N N N RN N NR R RO Z O N 2 3 N N N 187 HO3S H2N 186 R1 Cl F R= 2,4,5-Cl2 (HO3S)C6H2 R= SO3H; R1= CH3, CH2CH3; Z= linear R1= CH3; R2, R3= -CH2CH3 or branched C2-3 alkylene; m= 0-2

X N N N X N N N X N N N 188 189 190 CN O

X N N N X N N N Y Y 191 192 X1 X1, X3= H, Cl, SO3H X2 N N X2= H, SO3H X4= H, CH3, Ph X3 X4 N X5= H, CH3 193 X5 Fig. 24. Chemical structure of the Reactive dyes and dyes based on 4-aminoazobenzene.

Reactive dyes 184 (Fig. 24) are used for and the product was subjected to condensation dyeing -OH and –NHCO- containing fibers and with 5-chloro-2, 4, 6-trifluoropyrimidine to give they were prepared via condensation of 2-amino- dyes 186 [126]. 5-hydroxy-7-naphthalenesulfonic acid with The water soluble dye 187 (Fig. 24) was 5-chloro-4, 6-difluoropyrimidine followed by utilized for dyeing polyamide fibers. It was the azo-coupling of the product with 1-amino-4- synthesized by diazotization of 2, 4, 5-Cl (HO S) methoxy-2-benzenesulfonic acid [2]. 2 3 C6H2NH2 and azo-coupling with 4-amino-2- (diethylamino)-6-methylpyrimidine [127]. 4-HO3SCH2C6H4NH2 was diazotized and azo- coupled with 1-(2-sulfoethyl)barbituric acid to Conclusion offer greenish-yellow reactive dyestuff 185 for cotton fabrics [125] (Fig. 24). The preparation and chemistry of nitrogen- containing heterocyclic dyes have been broadly Compound 186 (Fig. 24) was used for dyeing investigated. Many derivatives of this class of both natural and synthetic polyamide and rayon materials were verified to be excellent dyestuffs. fibers. Thus, 4-nitrophenol-3-sulfonic acid was We introduced a systematic review of recently interacted with ethylene chlorohydrin to reduce synthesized 5 and 6 nitrogen-containing the nitro group. The produced amine intermediate heterocyclic dyes and their dyeing efficiency on a was then diazotized and azo-coupled with variety of textile fibers. 2-amino-5-hydroxy-7-naphthalenesulfonic acid

Egypt.J.Chem. 61, No. 5 (2018) 932 TAWFIK A. KHATTAB AND MOHAMED REHAN

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مراجعة حول تحضير األصباغ الغير متجانسة المحتوية على ذرة النيتروجين وتطبيقها علي االلياف النسيجية - الجزء 1: الحلقات الخماسية والسداسية الغير متجانسة

توفيق خطاب1 ومحمد ريحان2 1 قسم الصباغة والطباعة والمواد الوسيطة - شعبة بحوث الصناعات النسيجية - المركز القومي للبحوث - الدقي - القاهرة - مصر 2قسم التحضرات والتجهيزات لاللياف السيليلوزية - شعبة بحوث الصناعات النسيجية - المركز القومي للبحوث - الدقي - القاهرة - مصر

لقد ازدادت أهمية الصبغات غير المتجانسة في اآلونة األخيرة بسبب درجاتها اللونية العميقة ودرجة سطوعها وقوة ألوانها العالية وثباتها اللوني للغسيل والضوء والحرارة والعرق واالحتكاك وذلك مقارنة باألصباغ المماثلة المشتقة من البنزين. في هذه المراجعة ، نعطي تفاصيل توضح طرق التحضير المختلفة لألصباغ غير المتجانسة خماسية وسداسية الحلقة المحتوية علي ذرة النيتروجين وكذلك دراسة كفاءتها في صباغة ألياف النسيج.

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