A series of novel disperse azo dyes synthesis, based on 1-(4-N-acetyl amino) 2-methyl phenyl 2-chloro ethanone.

 

N. K. Prajapati¹*  and  Dr. D.G. Patel²

¹Department of Chemistry, M.N. College, Visnagar-384315, Gujarat, India.

²Department of Chemistry, Municipal Arts and Urban Bank Science College, Mehsana-384001, Gujarat, India.

*Corresponding Author E-mail: nkp15875@gmail.com

ABSTRACT:

 

 

INTRODUCTION:

Disperse dyes are coloured organic compound 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.

 

The increase of disperse azo dyes has been mainly due to the fact that during this  time the range of shades obtained with azo dyes has increased bathocromically. Today a large numbers of violet and blue disperse azo dyes are available. 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, of  some novel disperse azo dyes based on 1-(4-N-acetyl amino) 2-methyl phenyl 2-chloro ethanone.

 

MATERIALS AND METHODS:

All reagents were of analytical reagent grade and were used without further purification, All the product were synthesized and characterized by their spectral analysis, All Chemicals and solvents like acetone, ethanol, Methyl aniline, 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. Spectrophotometer and C, H, N of all disperse dyes were estimated by the means of a Carlo Erba Elemental Analyser (Italy)

 

EXPERIMENTAL:

Synthesis of  1-(4-N-acetyl amino-2-methyl phenyl) 2-(N-4 methyl phenyl amino) ethanone (A).

A mixture of 40 ml of anhydrous acetone and 1 ml of pyridine and methyl aniline in 250 ml flask then  added drop wise to a mixture of  (0.05M) 1-(4-N-acetyl amino) 2-methyl phenyl 2-chloro ethanone and sodium bicarbonate as an acid acceptor. The reaction mixture is set aside over night Then resultant product were 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 mass just alkaline with conc.NH₃ solution (d=0.880)  to give yield 1-(4-N-acetyl amino-2-methyl phenyl) 2-(N-4 methyl phenyl amino) ethanone (A).

 

Synthesis of  azo disperse dyes :

1-(4-N-acetyl amino-2-methyl phenyl) 2-(N-4 methyl phenyl amino) ethanone (A).

(0.01 mole) was dissolved in HCl (0.03 mole) with stirring and the solution was cooled to   0-5˙C in an ice-bath. A solution of sodium nitrite (0.01 mole) in 5 ml water cooled to 0˙c  then was added 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 reported method.^8-9

 

Table : I   Characterization of  novel azo disperse dyes :

Dye No	Molecular Formula	Mol. Wt (gm/mole)	Melting Point C	%  C		%  H		%  N
				Found	Cal	Found	Cal	Found	Cal
N-1	C26H29N4O3Cl	480.5	210	64.90	64.93	5.40	5.41	9.90	9.98
N-2	C27H32N4O3	460	240	70.40	70.43	6.93	6.95	12.07	12.17
N-3	C23H23N4O3	403	212	68.40	68.48	5.68	5.70	11.90	11.91
N-4	C25H25N4O3	429	180	69.90	69.93	5.80	5.82	13.00	13.05
N-5	C27H29N4O	425	240	76.10	76.23	6.80	6.82	13.12	13.17
N-6	C30H34N6O3	526	215	68.40	68.44	6.42	6.46	15.90	15.96

 

Table :  II   Position of selected bands in IR spectra of  Disperse Azo dyes :

Dye No.	C-H Stretching of aromatic cm-1	CH3 Stretching cm-1	CN Stretching cm-1	C=O (CH2OCOCH3) COCH2 Stretching cm-1	N=N Stretching cm-1	1,2,4-Tri Substituted cm-1	Tertiary amine cm-1	Primary Alcohol cm-1
N-1	3030, 1590,1480	-------	----------	-----------	1590 1610	1590,1620 1475,1520	1240,1290 3350,1590	1050, 1100 1350
N-2	2930,1610 1475,1470	2850,1475, 1320,1350	-----------	-------------	1600 1610	3100,1615, 1465	1240,1355 3410	1070,1350 1100
N-3	3030,1560 1630,1480	2830,1475, 1360	2240	1725	1630	1575 1640,1475	1350,1550 3450	1050,1100 1320,1350
N-4	2950,2990 1610,1480	2825,1480, 1350,1355	2220	1730	1630	3000,1550, 1640,1475	1280,1240 3350,1350	1050,1100 1275,1320
N-5	2950,1575 1610,1480	----------	2230	---------------	1575 1610	3000,1575 1475,1520	1240,1280 3450,1520	1050,1100 1260,1300
N-6	2930,1610 1480,1510	-----------	---------	1725	1610	3100,1610 1480,1510	1250,1520 3420	1050.1100 1260,1300

 

N1-N6 coupling component was dissolved in HCl (15 ml) and then solution cooled 0-5˙c  To this well stirred solution the above diazonium salt solution was added slowly so that temperature did not rise above 0-5˙c while maintaining the pH 4-5 by the action of sodium acetate solution(10% w/v) the mixture was stirred for 3 hrs. at 0-5˙c. After completion of the reaction the solid material was filtered, washed and dried it. So N1-N6 azo disperse dyes were prepared.

 

RESULTS AND DISCUSSION:

The  azo disperse dyes obtained  from this compounds are shown in Scheme-I  The 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 six series of disperse azo dyes contain aromatic nuclei, azo group and hydroxyl group. The band appeared from 1050 to 1350 cm^-1  due to primary –OH group, The bands at 1500, 1200 and 1050 cm^-1  appeared in the double bond region due to aromatic stretching. The strong  band at 1575 to 1630 cm^-1 appeared in the spectra

 

were considered for the presence of azo (-N=N-) group. The band of 1725 to 1730 cm^-1  might be responsible to –CO of –COCH₂ group. In the spectra of dyes obtained from methyl aniline derivatives side chain attached to the tertiary nitrogen the weak bands observed 2890-and 2950 cm^-1 which is attributed to the -CH₂ stretching vibration.

 

The IR spectra of all dyes comprise the important bands due to initial diazo component. The bends due to –CH3 stretching 2825-2850 and 1320-1475 cm^-1 and -CO of -COCH₂ dimethyl amine (-CH3). The other bands due to presence of coupling component are their respective positions.

 

CONCLUSION:

A series of azo disperse dyes have been prepared using based on 1-(4-N-acetyl amino) 2-methyl phenyl 2-chloro ethanone. So this disperse dyes give deeper shade and excellent light fastness and wash fastness properties. However, disperse dye can be used by even young children to make designs paper, which can then be transferred to polyester fabrics or other synthetics.

 

Reaction scheme-I

 

Where,

N-1		N-4
N-2		N-5
N-3		N-6

 

 

REFERENCES:

1.       G.H. Ellis and F.Brown, British Celanese ltd, Brit.pat. Dec.5,1934, 420,593.

2.       A.I.vogel, A Textbook of Practical Organic Chemistry,3^rd ed., Longman, London. 1961, p. 620

3.       P.F. Gorden, P. Gregory, Organic chemistry in colour,1^st ed. Springer- Verlag, Berlin, 1983,p.60

4.       S.K. Mohamed, A.M. Nour El-Din,J.Chem.Res.1999, 8,508.

5.       R.D.Naik,C.K.Desai,K.R.Desai,Orient.J.Chem.2000,16,159

6.       B.C.Dixit,H.M.Patel,D.J.Desai,J.serb.chem.soc.2007,72,119

7.       B.C. Dixit, H.M. Patel, D.J. Desai, R.B. Dixit, E-J. chem..2009,6, 315.

8.       M. Szymczyk, A.E. Shafei, H.S. Freeman, Dye Pign.2007, 8,72.

9.       H.E. Frirz-David, L. Blengy, Fundamental Process of Dye Chemistry,3^rd edition, Wiley, Newyork,1949,p.241.

 

 

 

Received on 09.01.2012         Modified on 12.02.2012

Accepted on 20.02.2012         © AJRC All right reserved