Jamonline / 2(3); 2012 / 244250 Research Article

D.G.Patel & N.K.Prajapati

Journal of Atoms and Molecules

An International Online Journal
ISSN 2277 1247

SYNTHESIS AND FASTNESS PROPERTIES OF SOME NOVAL DISPERSE AZO DYES D.G.Patel1, N.K.Prajapati*2 Department of Chemistry, Municipal arts and Urban bank Science College, Mehsana-384001, Gujarat, India. 2 Department of Chemistry, M.N. College, Visnagar-384315, Gujarat, India. Received on: 23-05-2012 Abstract: Some novel azo disperse dyes prepared N-[4-(chloroacetyl)-3-methylphenyl]acetamide was reacted with various aromatic amine. Then resultant product were hydrolysis to give yield 1-(4-acetamido)2-methylphenyl)-2-(N-arylamino)ethanone. Then diazotized by the standard procedure and coupling with N,N-Bis-hydroxy ethyl-3-chloro aniline. Thus a series of azo disperse dyes has been prepared. After syntheses compounds were characterized by chemical as well as instrumental methods like melting point, elemental analysis and IR spectral studies. Key Words: Disperse dyes, Hydrolysis, IR, fastness properties. Revised on: 04-06-2012 Accepted on: 14062012
1

Introduction: Disperse dyes are coloured organic compound * Corresponding author Prajapathi N.K, Email: nkp15875@gmail.com which are not completely insoluble in water and suitable for colouring hydrophobic fibers. The first member of the group of disperse dyes were introduced in 1924 by Baddiley and sheperdon of the british dye stuffs

corporation (Duranol dyes) and by Ellis of the british celanese company (SRA dyes)1 for dyeing it.

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Jamonline / 2(3); 2012 / 244250 Traditionally, azo dyes are the most important class of commercial dyes, occupying more than half of the dye chemistry, which contain phenols as intermediates.2-5 Hence ,in continuation of earlier work,6-7 the present communication comprises the synthesis,

D.G.Patel & N.K.Prajapati (chloroacetyl)-3-methylphenyl]acetamide were react with various aromatic amine (0.1 mole) and then hydrolysis by refluxing with 75 ml of ethanol containing 15 ml HCl for 4-5 hours The cool solution was diluted with water and was mase just alkaline with

characterization of some novel disperse azo dyes based on 4-(N-acetyl amino) 2-methyl phenacyl chloride. Materials and Methods: All reagents were of analytical reagent grade and were used without further purification, All the product were synthesized and

conc.NH3 solution (d=0.880) to give yield 1(4-amino-2-methyl arylamino)ethanone(A). Synthesis of azo disperse dyes : 1-(4-amino-2-methyl phenyl)-2-(Nphenyl)-2-(N-

arylamino)ethanone(A) was dissolved in HCl (0.03 mole) with stirring and this (X) solution was cooled to 0-50C in an ice-bath. A solution of sodium nitrite (0.01 mole) in 5ml water cooled to 00C then was added in solution (X). The excess nitrous acid was neutralized with sulfamic acid/urea (1.0 gms) and the mixture was filtered to get the clear diazonium salt solution. Diazotization of various aromatic amine was performed by areported method. 8-9 N,N-Bis-hydroxy ethyl-3-chloro aniline

characterized by their spectral analysis, All Chemicals and solvents like acetone,

Methanol, Aniline, Chloro aniline, p-toludine, p-anisidine, NaNO2, sodium acetate were purchased from S.D.fine chemicals (India). Melting points were taken in open capillary tube, IR spectra (KBr) were recorded on Perkin Elmer I.R. Spectrophotmeter and C,H,N of all disperse dyes were estimated by the means of a carlo Erba elemental analyser. Experimental: Synthesis of 1-(4-amino-2-methyl phenyl)2-(N-arylamino) ethanone (A). A mixture of 40 ml of anhydrous acetone and 1 ml of pyridine and chloro acetyl chloride in 250 ml flask then added drop wise to a mixture of N-(3-methylphenyl)acetamide and sodium bicarbonate as an acid acceptor. The reaction mixture is kept aside overnight. The resultant product (0.05M) N-[4-

coupling component was dissolved in HCl (15 ml) and then solution cooled 0-50C To this well stirred solution the above diazonium salt solution was added slowly so that temperature did not rise above 0-50C while maintaining the pH 4-5 by the action of sodium acetate solution(10% w/v) the mixture was stirred for 3 hrs. at 0-50C. After completion of the reation the solid material was filtered, washed and dried it. So some novel azo disperse dyes were prepared.

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Jamonline / 2(3); 2012 / 244250 Results and Discussion: The azo disperse dyes obtained from this compounds are shown in Scheme-I The 467

D.G.Patel & N.K.Prajapati nm in DMF. The values of the

logarithm of molar extinction coefficient (log ) of all the dyes were in the range of 3.1654.239 , consistent with their medium

elemental of C,H,N confirmed by Table: I The observed bands in the IR spectra for each dye are shown in Table-II IR spectra of all Five series of disperse azo dyes contain aromatic nuclei, azo group and hydroxyl group. The band appeared from 1050 to 1550 cm-1 due to primary OH group, The strong band at 1590 to 1630 cm1 appeared in the spectra are considered for the presence of azo (-N=N-) group. The band of 17001735 cm-1 might be responsible for CO of COCH2 group. In the spectra of dyes obtained from aromatic amine derivatives bearing a -hydroxy ethyl side chain attached to the tertiary nitrogen. The weak bands observed 2890 cm-1 and 2950 cm-1 is attributed to the -CH2 stretching vibration. The IR spectra of all dyes comprise the important bands due to initial diazo to CH3

absorption intensity The disperse azo dyes were applied at a 2% dye bath on nylon and polyester fabrics and give various shade

implied in Table-III. All the dyes D1 to D5 were applied on nylon and polyester fibers using the reported procedure 10-13 and the results of exhaustion and fixation of all the dyes on polyester and nylon fabrics are furnished in Table: IV-A and IV-B. Conclusion: The azo disperse dyes have been prepared using based on N-[4-(chloroacetyl)-3-

methylphenyl]acetamide The present study revealed that prepared azo disperse dyes showed dawn slow, Orange, yellow wide range of shades. They showed good dyeing performance on polyester and nylon fiber and The light fastness values of the azo disperse dyes are more consistent. Fastness properties: The light fastness of all the dyes rating 5 for nylon and polyester fabrics, which shows

component. The bends due

stretching 29303030 cm-1 The other bands due to presence of coupling component are their respective positions. The visible absorption spectroscopic

light fastness good for nylon and polyester. The wash fastness of all the dyes rating 4 for nylon and polyester fabrics, shows wash

properties of the all dyes were recorded in DMF. Absorption maximam ( max), Intensites ( log ), dyeing assessment of disperse azo dyes on polyester and Nylon fabrics are shown in Table-III, The absorption maxima (max) of all the dyes falls in the range 327-

fastness and of all the dyes Very good. Acknowledgement: Authors are thankful to The Head,

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Jamonline / 2(3); 2012 / 244250 Urban bank science college, Mehsana,

D.G.Patel & N.K.Prajapati

Gujarat for providing research facilities.

Reaction scheme-I
H3C ClCH 2COCl

NHCOCH

Chloro acetyl Chloride Anhydrous Acetone

N-(3-methylphenyl)acetamide

Sodium bicarbonated as an acid acceptor H3C

ClH2COC

NHCOCH 3

N-[4-(chloroacetyl)-3-methylphenyl]acetamide

Aromatic amine(-R) H3C

RNHCH 2CO

NHCOCH 3 1-(4-acetamido)-2-methyl phenyl)-2-(N-arylamino) ehtanone

Hydrolysis H3C Diazotisation

RNHCH 2CO H3C R -NHCH 2COHCl,NaNO
2

NH2

N=N-Cl

0-5 C Diazonium salt Coupling

1-(4-amino-2-methyl phenyl)-2-(N-arylamino) ehtanone

[N,N-Bisihydroxyethyl-3-chloro aniline] Where R= (i) Aniline (ii) 4-methyl aniline (iii) 4-Chloro aniline
Cl
RNHCH
2CO

H3C
CH 2-CH 2-OH

N=N-

N
CH 2-CH 2-OH

(IV) 4-methoxy aniline (v) 4-isopropyl aniline Azo disperse dye

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Jamonline / 2(3); 2012 / 244250 Table : I Characterization of novel azo disperse dyes :

D.G.Patel & N.K.Prajapati

No D-1 D-2 D-3 D-4 D-5

Molecular Formula C25H27N4O3Cl C26H29N4O3Cl C25H26N4O3Cl2 C26H29N4O4Cl C28H33N4O3Cl

Mol.Wt (gm/mole) 466.5 480.5 501 496.5 508.5

Melting Point C 230 210 170 109 171

% Found 63.4 64.90 59.66 62.92 65.84

C Cal 63.64 64.93 59.76 92.95 65.94

% H Found Cal 5.3 5.52 5.40 5.41 5.10 5.17 6.30 6.33 6.40 6.47

% N Found Cal 12.2 12.32 9.90 9.98 11.10 11.15 10.40 10.49 10.90 10.99

Table: II Position of selected bands in IR spectra of Disperse Azo dyes: Dye No. D-1 D-2 D-3 D-4 C-H Stretching of aromatic cm-1 3030, 1600,1480 3030, 1590,1480 2950, 1580,1480 2930, 1590,1480 2930, 1600,1480 N=N Stretching cm-1 1600 1630 1590 1610 1590 1600,1630 1,2,4-Tri Sustituted cm-1 1590,1640 1475,1510 1590,1620 1475,1520 3150,1580 1490 1590,1640 1475,1510 1580,1625 1475,1510 Tritiary amine cm-1 1240,1280 3420 1240,1290 3350,1590 1230,1280 1350 1240,1280 3420 1230,1280 3410 Primary alcohol cm-1 1050,1130 1270,1550 1050,1100 1350 1050,1100 1260,1300 1050,1130 1270,1550 1050,1130 1260,1540

D-5

1600 1620

All thes spectra comparised the bands around 2890 and 2950 cm-1 presented of -CH2 of -COCH2 group

Table: III Absorption maximam (max), Intensites (log ), Acid azo dyes on Wool and Nylon fabrics: Dyeing properties max Dyeing on Polyester Dyeing on nylon Dye Log Shade (nm) Light Wash Light Wash fastness fastness fastness fastness D-1 327.0 3.165 Dawn slow 5 4 5 4 D-2 467.0 4.208 Orange 5 4 5 4 D-3 464.0 4.239 Orange 5 4 5 4 D-4 458.0 4.052 Orange 5 4 5 4 D-5 338.0 3.998 Yellow 5 4 5 4 Light fastness: 1-poor, 2-slight, 3-moderate, 4-fair, 5-good, 6-very good. Wash fastness: 1-poor, 2-fair, 3-good, 4-very good, 5-excellent.

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Jamonline / 2(3); 2012 / 244250 Table: IV-A

D.G.Patel & N.K.Prajapati

Exhaustion and Fixation study of Disperse azo dyes: Fabric under study: Nylon Dye Under study : 40.0 mg MLR : 50: 1 Amount of dye exhausted from dye bath b=(40-a) mg 31.30 31.48 30.88 31.325 30.06 % of dye exhausted from dye bath (100 ) 40 78.25 78.7 77.2 78.31 75.15 Amount of dye present on dye pattern c mg 21.57 21.43 21.42 21.99 20.56 % of fixation 100 68.91 68.07 69.36 70.19 68.46

Dye

Amount of dye left in dye bath a mg 8.70 8.52 9.12 8.675 9.24

D-1 D-2 D-3 D-4 D-5

Table: IV-B

Exhaustion and Fixation study of Disperse azo dyes: Fabric under study: Polyester Dye Under study : 40.0 mg MLR : 50: Amount of dye % of dye exhausted exhausted from from dye bath (100 ) dye bath b=(40-a) mg 40 31.79 79.47 32.46 81.15 32.08 80.2 31.85 79.63 32.32 80.8 Amount of dye present on dye pattern c mg 24.86 20.15 21.42 22.4 21.90 % of fixation 100 78.20 62.07 66.77 70.32 67.75

Dye

Amount of dye left in dye bath a mg 8.21 7.54 7.92 8.15 7.68

D-1 D-2 D-3 D-4 D-5

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Jamonline / 2(3); 2012 / 244250 References: 1 G.H. Ellis and F.Brown,British Celanese ltd, Brit.pat. 420,593.( Dec.5,1934). 2 A.I.vogel, organic A textbook of practical

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Society,72(2),119-127. 8 Dixit B.C., Patel H.M., Desai D.J., Dixit R.B.,(2009). Azo Dyes and Mordent Acid Azo Dyes Based on 2,4-Dihydroxy benzophenone, E-Journal of

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