Synthesis, characterization and printing application of solvent dyes based on 2-hydroxy-4-n-octyloxybenzophenone

Article abstract of DOI:10.1155/2011/862929

Solvent dyes have been prepared by the coupling of diazo solution of different aromatic amines with 2-hydroxy-4-n-octyloxybenzophenone. The resultant dyes were characterized by elemental analysis as well as IR and 1H NMR spectral studies. The UV-Visible s

Full text of DOI:10.1155/2011/862929

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
2011, 8(2), 615-620
http://www.e-journals.net
Synthesis, Characterization and Printing
Application of Solvent Dyes Based on
2-Hydroxy-4-n-octyloxybenzophenone
BHARAT C. DIXIT* and HITENDRA M. PATEL
Department of Chemistry, V. P. & R. P. T. P. Science College
Vallabh Vidyanagar-388120, Gujarat, India
dixits20002003@yahoo.co.in
Received 21 September 2010; Accepted 22 November 2010
Abstract: Solvent dyes have been prepared by the coupling of diazo solution
of different aromatic amines with 2-hydroxy-4-n-octyloxybenzophenone. The
resultant dyes were characterized by elemental analysis as well as IR and
1H NMR spectral studies. The UV-Visible spectral data have also been
discussed in terms of structure property relationship. The printing of all the dyes on
cotton fiber was monitored. The result shows that better hue was obtained on
printing on cotton fiber and it is resulted in yellow to reddish brown colorations
which showed a good fastness to light, with poor to good fastness to washing,
perspiration and sublimation, however it shows poor rubbing fastness.
Keywords: Solvent dyes, Printing application, Cotton fibre, Light fastness, Washing fastness.
Introduction
Whilst phenols are well established intermediates for the syntheses of various commercial
dyes1-6, they are marketed in the form of azo disperse, azo-acid dyes etc. All of these dyes
having phenolic moiety, containing hydroxyl group as an auxochrome group. Such
auxochromic(-OH) and chromophoric(C=O) group containing compound i.e. 2-hydroxy-4-
n-octyloxybenzophenone has shown wide applications as a polymer additives7-9. It is an
excellent UV absorber10, which prevents the photo degradability of most of vinyl
polymers11-13. The area in which the acid azo dyes and mordent azo dyes formation based on
this compound has not been developed except of few patents14-17.
The formation of solvent dyes based on this compound may yield the dyes with good
hue properties. Hence, in continuation of our earlier work18, it was thought interesting to
explore the field of acid azo dyes based on 2-hydroxy-4-n-octyloxybenzophenone. Thus, the
present communication comprises the printing application of solvent dyes based on
2-hydroxy-4-n-octyloxybenzophenone.

616
BHARAT C. DIXIT et al.
Experimental
All the chemicals used were of analytical grade and were further purified as and when required. The
aromatic amines listed in Scheme 1 were used for diazotization. Cotton fibers were gifted by color
tax (Pvt) Ltd, Surat. Melting points were determined by open capillary method and are uncorrected.
The visible absorption spectra were measured on a Carl Zeiss UV/VIS Specord spectrometer and
elemental analysis was carried out on Perkin Elmer CHNS/O Analyzer 2400 Series II. Infrared
spectra were recorded in KBr pellets on a Perkin-Elmer Spectrum GX FT-IR model, proton NMR
spectra were recorded on Hitachi R-1500 in DMSO-D6 solvent and TLC (Thin layer
chromatography) was run on a aluminum sheets precoated with silica gel 60 F245, (Merck, Germany)
using methanol-water-acetic acid (12:3:7) solvent system. Colour spot was visualized by UV
chamber. Printing machine (Process controller PC2F/R) was used for printing purpose.
Synthesis of solvent dyes
Diazotization
Diazotization of various aromatic amines 1(a-g) (Scheme 1) was carried out by the method
reported in literature19,20. Accordingly each of the aromatic amines 1(a-g) (3.19x10-3 kg,
0.01 mol) was mixed with HCl (2.5x10-5 m3, 37%) in a mortar, transferred to a 3-neck round
bottom flask and additional HCl (2.0x10-5 m3, 37%) was added. To the resultant suspension
crushed ice (25x10-3 kg) and NaNO2 (2.5x10-5 m3, 4N) were added. Diazotization was
carried out over 0.5 h at 5 0C with constant stirring.
+
-
NaNO2, HCl
0-50C
Ar
N
N
C l
Ar
NH2
Diazonium salts
Aromatic amine
(a-j)
O
C
0-50C
NaOH
+
OH
OC8H17
O
C
OH
Ar
N
N
OC8H17
Dyes(D1-D7)
Dyes No
R1
NO2
H
R2
H
R3
H
R4
H
H
H
Amines (a-j)
2- Nitroaniline
4- Nitroaniline
3 -Nitroaniline
D1
D2
D3
D4
D5
D6
D7
H
NO2
H
H
Cl
NO2
H
NO2 Cl 2,6 -Dichloro-4-nitroaniline
CH3
H
H
H
CH3
H
Cl
H
H
H
2,4-Dimethylaniline
3-Chloroaniline
4-Chloroaniline
Cl
H
Scheme 1. Proposed synthetic rout for the preparation of solvent dyes

Synthesis, Characterization and Printing Application
617
Coupling procedure
The coupling of above mentioned diazotized aromatic amines 1(a-g) was carried out in the
similar manner. The general procedure followed is given below: 2-Hydroxy-4-n-
octyloxybenzophenone (2.15x10-3 kg, 0.01 mol) was dissolved in sodium hydroxide
(1.2x10-5 m3, 0.01 mol) solution. The clear solution was cooled in ice-bath and diazonium
solution of aromatic amines 1(a-g) was added drop wise over a period of 30 min with
vigorous stirring. The pH was maintained between 2.0 to 3.0 by simultaneous addition of 10%
w/v sodium carbonate solution. Stirring was continued for 2 h, allowing the temperature to
rise to ambient. The dyes was then filtered off and dissolved in distilled water after that
solvent dyes were obtained by evaporation procedure and it was dried at room temperature.
The dyes were designated as solvent dye (D1-7) and were recrystalised in acetone.
Printing on cotton fiber
Solvent dyes (D1-D7) used for printing of cotton fiber was carried out by the method
reported in literature21.
Characteristic data of solvent dyes
1-[2-Hydroxy-4-n-octyloxy -5-(2-nitrophenylazo)phenyl]-1-phenylmethanone (D1)
0
Calculated for C27H29O5N3: M. wt.: 475, % yield: 88, m. p.: 47-49 C, Rf value: 0.82; C,
68.21%; H, 6.10%; N, 8.84%. Found: C, 68.19%; H, 5.98%; N, 8.81%. IR: 3463 cm-1
(-OH); 3072 cm-1 (=CH, aromatic); 1628 cm-1 (C=O, diaryl); 1521 cm-1 (N=N); 1481 cm-1
(C=C, aromatic); 1333 cm-1 (C-N); 1101 cm-1 (C-O); 1212-1024 cm-1 (C-O-C, stretching);
1
732 cm-1, 584 cm-1, 481 cm-1 (for substituted benzene). H NMR: 10.7 δ (Ar-OH, singlet),
7.2-7.4 δ (Ar-H, multiplet), 3.6 δ (-OC8H17, singlet, 3H), 2.8 δ (–CH2-, multiplet), 2.23 δ
(-CH3, singlet, 3H), 1.8 δ and 1.2 δ (triplet,-CH3 and –CH2-).
1-[2-Hydroxy-4-n-octyloxy -5-(4-nitrophenylazo)phenyl]-1-phenylmethanone (D2)
0
Calculated for C27H29O5N3: M. wt.: 475, % yield: 92, m. p.: 52-54 C, Rf value: 0.80; C,
68.21%; H, 6.10%; N, 8.84%. Found: C, 68.17%; H, 5.94%; N, 8.78%. IR: 3450 cm-1
(-OH); 3082 cm-1 (=CH, aromatic); 1624 cm-1 (C=O, diaryl); 1522 cm-1 (N=N); 1490 cm-1
(C=C, aromatic); 1345 cm-1 (C-N); 1101 cm-1 (C-O); 1032 cm-1, 1211-1021 cm-1 (C-O-C,
1
stretching); 744 cm-1, 564 cm-1, 478 cm-1 (for substituted benzene). H NMR: 10.6 δ
(Ar-OH, singlet), 7.1-7.3 δ (Ar-H, multiplet), 3.8 δ (-OC8H17, singlet, 3H), 2.4 δ (–CH2-,
multiplet), 2.13 δ (-CH3, singlet, 3H), 1.6 δ and 1.4 δ (triplet,-CH3 and –CH2-).
1-[2-Hydroxy-4-n-octyloxy -5-(3-nitrophenylazo)phenyl]-1-phenylmethanone (D3)
0
Calculated for C27H29O5N3: M. wt.: 475, % yield: 87, m. p.: 50-53 C, Rf value: 0.85; C,
68.21%; H, 6.10%; N, 8.84%. Found: C, 68.15%; H, 5.96%; N, 8.76%. IR : 3481 cm-1
(-OH); 3070 cm-1 (=CH, aromatic); 1632 cm-1 (C=O, diaryl); 1542 cm-1 (N=N); 1483 cm-1
(C=C, aromatic); 1337 cm-1(C-N); 1103 cm-1 (C-O); 1212-1020 cm-1 (C-O-C, stretching);
1029 cm-1, 737 cm-1, 562 cm-1, 472 cm-1 (for substituted benzene). 1H NMR: 10.9 δ (Ar-OH,
singlet), 7.1-7.3δ (Ar-H, multiplet), 3.7 δ (-OC8H17, singlet, 3H), 2.6 δ (–CH2-, multiplet),
2.27 δ (-CH3, singlet, 3H), 1.4 δ and 1.1 δ (triplet, -CH3 and –CH2-).
1-[2-Hydroxy-4-n-octyloxy-5-(2,5-dichloro-4-nitrophenylazo)phenyl]-1-
phenylmethanone (D4)
0
Calculated for C27H27O5N3Cl2: M. wt.: 544, % yield: 78, m. p.: 66-69 C, Rf value: 0.87; C,
59.55%; H, 4.96%; N, 7.72%. Found: C, 59.49%; H, 4.92%; N, 7.68%. IR : 3633 cm-1
(-OH); 3080 cm-1 (=CH, aromatic); 1652 cm-1 (C=O, diaryl); 1532 cm-1 (N=N); 1473 cm-1

618
BHARAT C. DIXIT et al.
(C=C, aromatic); 1338 cm-1 (C-N); 1104 cm-1 (C-O); 1210-1021 cm-1 (C-O-C, stretching);
1
1032 cm-1, 782 cm-1, 741 cm-1, 583 cm-1, 485 cm-1 (for substituted benzene). H NMR: 10.6
δ (Ar-OH, singlet), 7.3-7.7 δ (Ar-H, multiplet), 3.5 δ (-OC8H17, singlet, 3H), 2.4 δ (–CH2-
,multiplet), 2.24 δ (-CH3, singlet, 3H), 1.6 δ and 1.4 δ (triplet,-CH3 and –CH2-).
1-[2-Hydroxy-4-n-octyloxy-5-(2,4-dimethylphenylazo)phenyl]-1-
phenylmethanone (D5)
0
Calculated for C29H34O3N2: M. wt.: 458, % yield: 82, m. p.: 45-47 C, Rf value: 0.86; C,
75.98%; H, 7.42%; N, 6.11%. Found: C, 75.94%; H, 7.39%; N, 6.08%. IR : 3580 cm-1
(-OH, phenolic); 3070 cm-1 (=CH, aromatic); 1621 cm-1 (C=O, diaryl); 1531 cm-1 (N = N);
1482 cm-1 (C=C, aromatic); 1463 cm-1 (C-N); 1338 cm-1 (C-O); 1210-1023 cm-1 (C-O-C,
stretching), 1034 cm-1, 1103 cm-1, 732 cm-1, 574 cm-1, 473 cm-1 (for substituted benzene).
1H-NMR: 10.6 δ (Ar-OH, singlet), 7.2-7.6 δ (Ar-H, multiplet), 3.4 δ (-OC8H17, singlet, 3H),
2.5 δ (–CH2-, multiplet), 2.21 δ (-CH3, singlet, 3H), 1.6 δ and 1.3 δ (triplet,-CH3 and –CH2-).
1-[2-Hydroxy-4-n-octyloxy -5-(3-chlorophenylazo)phenyl]-1-phenylmethanone (D6)
0
Calculated for C27H29O3N2Cl: M. wt.: 464, % yield: 76, m. p.: 55-58 C, Rf value: 0.83; C,
69.82%; H, 6.25%; N, 6.03%. Found: C, 69.78%; H, 6.21%; N, 5.97%. IR : 3430 cm-1 (-OH,
phenolic); 3540 cm-1 (-OH, acidic); 3062 cm-1 (=CH, aromatic); 1634 cm-1 (C=O, diaryl); 1581
cm-1 (N=N); 1483 cm-1 (C=C, aromatic); 1352 cm-1 (C-N); 1103 cm-1 (C-O); 1210-1022 cm-1
(C-O-C, stretching); 783 cm-1, 741 cm-1, 583 cm-1, 482 cm-1 (for substituted benzene).
1H NMR: 10.8 δ (Ar-OH, singlet), 7.3-7.5 δ (Ar-H, multiplet), 3.7 δ (-OC8H17, singlet, 3H),
2.5 δ (–CH2- ,multiplet), 2.27 δ (-CH3, singlet, 3H), 1.9 δ and 1.3 δ (triplet,-CH3 and –CH2-).
1-[2-Hydroxy-4-n-octyloxy-5-(4-chlorophenylazo)phenyl]-1-phenylmethanone (D7)
0
Calculated for C28H32O3N2: M. wt.: 444, % yield: 85, m. p.: 43-46 C, Rf value: 0.85; C,
75.67 %; H, 7.20 %; N, 6.30 %. Found: C, 75.62 %; H, 7.17 %; N, 6.27 %. IR : 3590 cm-1
(-OH); 3063 cm-1 (=CH, aromatic); 1632 cm-1 (C=O, diaryl); 1533 cm-1 (N=N); 1471 cm-1
(C=C, aromatic); 1324 cm-1 (C-N); 1103 cm-1 (C-O); 1211-1023 cm-1 (C-O-C,
stretching);1031 cm-1, 780 cm-1, 744 cm-1, 586 cm-1, 475 cm-1 (for substituted benzene).
1H NMR: 10.6 δ (Ar-OH, singlet), 7.1-7.6 δ (Ar-H, multiplet), 3.8 δ (-OC8H17, singlet, 3H),
2.6 δ (–CH2-, multiplet), 2.24 δ (-CH3, singlet, 3H), 1.7 δ and 1.4 δ (triplet,-CH3 and –CH2-).
Fastness property
The fastness to light, sublimation and perspiration of dye pattern was assessed according to
British standard: 1006-1978 and the wash fastness test according to Indian standard: IS:
765-1979. The rubbing fastness was tested by using Crock meter (Atlas) AATCC-1961,
shown in Table 2.
Determination of the percentage exhaustion and fixation
The dye bath percentage exhaustion and fixation of the dyed fabric was determined
according to the known method22 and is shown in Table 1.
Results and Discussion
Physical properties of solvent dyes
All the dyes are obtained as crystal powder ranging from yellow to reddish brown in colours. The
purity of the dyes were checked by TLC using methanol-water-acetic acid (12:3:7) solvent
system. The TLC results show that only single spot observed for each dye. The purified dyes
have melting point measured by open capillary tube. The melting points were uncorrected.

Synthesis, Characterization and Printing Application
619
The results of elemental analysis content of each dyes are consistent with the predicted
structure as shown in Scheme 1. The number of azo group is almost one for each dye. The
nitrogen content and number of azo group for each dye are co-related with each other. The
IR spectrum of each dye comprises the important features of aromatic, azo, hydroxyl, alkoxy
and keto groups. The 1H NMR spectra of all the diazo compounds based on 2-hydroxy-4-n-
octyloxybenzophenone shows an important signals at their respective positions confirmed
the structures of various dyes as shown in Scheme 1.
The visible absorption spectroscopic properties of dyes were recorded in double distilled
water. The absorption maxima (λmax) of all the dyes fall into the range of 346-410 nm in water,
as shown in Table 1. The value of the logarithm of molar extinction coefficient (log ε) of all
the dyes were in the range of 4.11 – 4.28, consistent with their high intensity of absorption.
Table 1. Absorption maxima (λmax), intensities (log ε), exhaustion (E) and fixation (F) of
solvent dyes on cotton
Dyes
No.
D1
Absorption maxima
Intensities
Log ε
4.216
4.193
4.167
4.280
4.117
4.172
4.185
Printing on Cotton
%E
80
75
72
85
74
71
85
%F
89
94
90
89
86
88
92
λmax/nm In DMF
346
352
385
349
385
410
397
D2
D3
D4
D5
D6
D7
Moreover, the presence of electron donating or electron attracting groups did not bring
about any marked increase or decreased in λmax in the visible region and that log ε remained
nearly constant. However, electron attracting substituents like –NO2 and -Cl in the
substituent group of the coupler increase polarizability, and will results in bathochromic
shifts. This leads to decrease in energy between the highest occupied molecular orbital and
lowest unoccupied molecular orbital and thus π
lower frequency photon, resulting in the bathochromic shift of the visible absorption band.
π* electronic transition takes place at
Dyeing properties of dyes
The solvent dyes were applied at 2% depth on cotton fabric respectively. Their printing
properties are given in Table 2. These dyes gave a wide range of colours varying from
yellow to reddish brown shades with good levelness, brightness and depth on the fabrics.
Table 2. Results of solvent dyes on printing and various fastness properties of dyes on cotton
Perspiration
fastness
Acid Alkaline
Rubbing
fastness
Dry Wet
Dyes Color shades on Light Washing
No.
Sublimation
fastness
cotton
fastness fastness
D1
D2
D3
D4
Orange brown
Reddish brown
Reddish orange
Light yellow
5
5
5
4
4
5
5
5
4
5
5
4
5
4
4
4
5
4
5
5
5
5
4
5
5
5
5
5
4
4
5
4
4
5
4
4
4
4
4
4
4
4
4
4
4
3
4
3
4
D5 Chocolate brown
D6
D7
Yellow
Yellow

620
BHARAT C. DIXIT et al.
The variation in the shades of the dye fabric results from both the nature and position of
the substituent present on the diazotized compound. The dyeing showed an excellent
fastness to light, with very good to excellent fastness to washing, perspiration and
sublimation, however it shows poor rubbing fastness. A remarkable degree of levelness after
washing is observed. This may be attributed to good penetration and affinity of the dye
molecule in to fiber structure.
Conclusion
Produced solvent dyes have good fastness to light but show poor sublimation and rubbing
fastness properties. The nature of the substituent in the coupling components has a little influence
on the visible absorption and shade of the printing. All the solvent dyes show a good solubility in
various organic solvents therefore, they may be useful as fuel dye and in printing ink.
Acknowledgment
The authors are thankful to the principal, for providing necessary research facilities. Authors
are also thankful to Mr. Ashok C. Kapadia, Mr. Pradeep N. Mistry of Color Tax (Pvt) Ltd.,
Surat for characterization of azo group and giving the standard of fastness properties and
Raju Mehta of G.P.C.B., Surat for providing useful chemicals.
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