Dyes and Pigments 160 (2019) 524–529

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Dyes and Pigments

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Facile synthesis of novel disperse azo dyes with aromatic hydroxyl group T
∗
Jinjing Qiu, Jinqiu Xiao, Bingtao Tang , Benzhi Ju, Shufen Zhang
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: A series of novel disperse azo dyes containing aromatic hydroxyl group were synthesized by a novel and simple
Aromatic hydroxyl compounds synthetic strategy, in which, the stable solid diazonium salts of weakly basic amines were used to couple with
Azo-coupling reactions aromatic hydroxyl compounds in alkaline aqueous solution. The experimental procedure was simple and had a
Disperse azo dyes high reaction rate and excellent yields. The structures of the dyes were confirmed by HRMS, FT-IR, 1H NMR, and
Weakly basic amines
elemental analysis. Then, the synthesized azo dyes were used for dyeing polyester fabric and gave favorable
Dyeing
color fastness that was comparable with that of commercial dyes.

1. Introduction
Azo dyes are used widely for dyeing textiles [1–3] and involved in
nearly all dye categories, such as direct, reactive, and disperse dyes
[4–6]. The molecule of azo dye contains one or more D–π –A systems,
which can produce diverse colors by changing the electron-donating
(D) or electron-accepting (A) functional groups [7,8].
Azo dyes produced from weakly basic amines are widely adopted as
disperse dyes to dye synthetic fiber [9,10]. Such dyes have more than
one strong electron withdrawing groups in their structures, which can
provide dark shades and enhance color fastness. Traditionally, weakly
basic amines are diazotized in concentrated sulfuric acid, and the
subsequent coupling process can proceed only under acidic conditions
[11–13]. Obtaining the structure that contains all the segments of
weakly basic amines and aromatic hydroxyl compounds is difficult
because the coupling reaction must be performed in alkaline aqueous
solution.
Azo dyes with aromatic hydroxyl group are constantly used in the
textile industry as water-soluble dyes, such as acid or reactive dyes for
dyeing protein or cellulosic fibers [14–16], and they are widely adopted
as colorant in foodstuffs, cosmetics, and drugs, or organic pigment for
ink-jet printing, painting, and so on [17–20]. The syntheses of these
dyes need to be conducted under alkaline conditions and the diazo
components are primary amines with strong basicity as their diazoti-
zation can proceed in diluted hydrochloric acid [21–24]. Nevertheless,
there is rare azo dyes with aromatic hydroxyl group in disperse dyes.
The diazo components used for the preparation of disperse azo dyes are
always weakly basic amines and their diazotizations are processed in
concentrated sulfuric acid. It is difficult for the diazonium salts to react
with aromatic hydroxyl compounds in alkaline aqueous solution as
large amounts of waste inorganic salt and strong heat of neutralization
and dilution will be produced [25,26].
In our recent research, stable solid diazonium salts of weakly basic
amines were obtained in organic solvent using 1,5-naphthalenedi-
sulfonic acid as stabilizer, and they were separated from the acidic
diazotization solution [27]. In this work, these diazonium salts were
reacted conveniently with coupling components containing aromatic
hydroxyl group to synthesize novel disperse azo dyes giving excellent
yields. The generation of large amounts of inorganic salt and strong
heat, as in the traditional method, was prevented. The dyeing proper-
ties of these dyes on the polyester fabric were satisfactory so that they
are suitable for dyeing as industrial disperse dyes.
2. Experimental
2.1. General information
1-phenyl-3-methyl-2-pyrazolin-5-one and 2-naphthol were bought
from Sinopharm Group Co., Ltd. Dispersing agent NNO (a mixture of
salts of multicore condensate aromatic sulfonic acids) was bought from
Zhejiang Jihua Group Co. Ltd. C. I. Disperse Yellow 163 (Y163) and C. I.
Disperse Orange 30 (O30) were purchased from Zhejiang Longsheng
Group Co., Ltd.
The purity of dyes was determined through standard curve obtained
in ethyl acetate using an Agilent 8453 Spectroscopy System. HRMS
were obtained by a LTQ Orbitrap XL™ instrument. Elemental analyses
were recorded on a Vario EL III Analyzer. 1H NMR spectra were ob-
tained by a Bruker Avance III spectrometer with TMS as the internal
standard. FT-IR spectra were measured on a Nicolet 6700 spectrometer
with KBr pellets.

∗
Corresponding author.
E-mail address: tangbt@dlut.edu.cn (B. Tang).

https://doi.org/10.1016/j.dyepig.2018.08.052
Received 4 June 2018; Received in revised form 30 July 2018; Accepted 27 August 2018
Available online 29 August 2018
0143-7208/ © 2018 Elsevier Ltd. All rights reserved.
J. Qiu et al.
2.2. Typical preparation of disperse azo dyes
The diazonium salts were prepared as stable solids in organic sol-
vent using published method [27]. Typical coupling process is de-
scribed as follows:
5 mmol 2-naphthol were dissolved in 50 ml water using 10 wt %
sodium hydroxide solution adjusting pH to 10–11. The temperature was
cooled to 0 °C–5 °C using ice-water bath. 5 mmol 2,4-dinitrobenzene
diazonium salt prepared freshly were slowly added in for about 1 h with
vigorously stirring and the pH was maintained in 10–11 using 10 wt %
sodium hydroxide solution. Color reaction with H-acid was used to
confirm the reaction endpoint. The dye was filtered, washed and dried
by oven at 70 °C to afford the product.
2.3. Characterization of the dyes
Compound 4a: C16H12N6O5: HRMS, m/z: calcd for [M-H]-,
367.0796; found, 367.0787. 1H NMR (500 MHz, DMSO‑d6) δ (ppm):
14.56 (s, 1H), 8.96 (s, 1H), 8.63 (d, J = 9.4 Hz, 1H), 8.36 (d,
J = 9.2 Hz, 1H), 7.91 (d, J = 7.9 Hz, 2H), 7.56–7.46 (m, 2H), 7.29 (d,
J = 6.3 Hz, 1H), 2.39 (s, 3H). FT-IR (KBr, cm−1): 3423, 3105, 2924,
1673, 1614, 1601, 1575, 1523, 1492, 1421, 1374, 1344, 1324, 1313,
1270, 1208, 1153, 1139, 1125, 1002. Anal. Calcd: C, 52.18; H, 3.28; N,
22.82%. Found: C, 52.03; H, 3.01; N, 22.43%.
Compound 4b: C17H12N6O3: HRMS, m/z: calcd for [M-H]-,
347.0898; found, 347.0887. 1H NMR (500 MHz, DMSO‑d6) δ (ppm):
13.60 (s, 1H), 8.84 (d, J = 2.5 Hz, 1H), 8.56 (d, J = 8.5 Hz, 1H), 8.05
(d, J = 9.3 Hz, 1H), 7.90 (d, J = 8.2 Hz, 2H), 7.50 (t, J = 7.8 Hz, 2H),
7.28 (t, J = 7.5 Hz, 1H), 2.36 (s, 3H). FT-IR (KBr, cm−1): 3418, 3086,
2923, 2228, 1667, 1615, 1570, 1537, 1519, 1494, 1459, 1338, 1278,
1248, 1219, 1181, 1147, 1077, 1046. Anal. Calcd: C, 58.62; H, 3.47; N,
24.13%. Found: C, 58.81; H, 3.06; N, 24.07%.
Compound 4c: C16H11Cl2N5O3: HRMS, m/z: calcd for [M-H]-,
390.0166; found, 390.0155. 1H NMR (400 MHz, DMSO‑d6) δ (ppm):
8.46 (s, 2H), 7.90 (d, J = 8.1 Hz, 2H), 7.57–7.41 (m, 2H), 7.27 (s, 1H),
2.28 (s, 3H). FT-IR (KBr, cm−1): 3420, 3089, 2972, 2923, 1664, 1595,
1558, 1526, 1504, 1442, 1389, 1374, 1333, 1311, 1252, 1192, 1144,
1078, 1049, 1010. Anal. Calcd: C, 49.00; H, 2.83; N, 17.86%. Found: C,
48.88; H, 2.57; N, 17.67%.
Compound 4d: C16H11Br2N5O3: HRMS, m/z: calcd for [M-H]-,
479.9135; found, 479.9119. 1H NMR (400 MHz, DMSO‑d6) δ (ppm):
8.60 (s, 2H), 7.90 (d, J = 8.1 Hz, 2H), 7.49 (t, J = 7.9 Hz, 2H), 7.26 (t,
J = 7.4 Hz, 1H), 2.30 (s, 3H). FT-IR (KBr, cm−1): 3420, 3082, 2922,
1663, 1586, 1556, 1517, 1431, 1373, 1331, 1306, 1248, 1189, 1147,
1130, 1077, 1048, 1007. Anal. Calcd: C, 39.94; H, 2.30; N, 14.56%.
Found: C, 39.97; H, 1.95; N, 14.54%.
Compound 4e: C16H12ClN5O3: HRMS, m/z: calcd for [M-H]-,
356.0556; found, 356.0548. 1H NMR (400 MHz, DMSO‑d6) δ (ppm):
13.59 (s, 1H), 8.51 (d, J = 2.5 Hz, 1H), 8.34 (dd, J = 9.1, 2.5 Hz, 1H),
8.02 (d, J = 9.1 Hz, 1H), 7.90 (d, J = 8.1 Hz, 2H), 7.49 (t, J = 7.8 Hz,
2H), 7.27 (t, J = 7.4 Hz, 1H), 2.36 (s, 3H). FT-IR (KBr, cm−1): 3421,
3096, 2972, 1668, 1595, 1568, 1525, 1502, 1460, 1437, 1372, 1336,
1272, 1239, 1216, 1179, 1151, 1116, 1048, 1000. Anal. Calcd: C,
53.72; H, 3.38; N, 19.58%. Found: C, 53.51; H, 3.00; N, 19.34%.
Compound 4f: C16H10N4O5: HRMS, m/z: calcd for [M-H]-, 337.0578;
found, 337.0571. 1H NMR (500 MHz, DMSO‑d6) δ (ppm): 16.35 (s, 1H),
8.97 (d, J = 2.7 Hz, 1H), 8.69 (d, J = 9.3 Hz, 1H), 8.59 (d, J = 9.8 Hz,
1H), 8.47 (d, J = 7.8 Hz, 1H), 7.97 (d, J = 9.8 Hz, 1H), 7.73 (d,
J = 7.7 Hz, 1H), 7.65 (t, J = 7.7 Hz, 1H), 7.61–7.55 (m, 1H), 6.68 (d,
J = 9.8 Hz, 1H). FT-IR (KBr, cm−1): 3442, 3111, 1611, 1589, 1528,
1494, 1481, 1448, 1401, 1341, 1259, 1181, 1132, 1094. Anal. Calcd: C,
56.81; H, 2.98; N, 16.56%. Found: C, 56.30; H, 2.43; N, 16.36%.
Compound 4g: C17H10N4O3: HRMS, m/z: calcd for [M-H]-,
317.0680; found, 317.0670. 1H NMR (400 MHz, DMSO‑d6) δ (ppm):
16.06 (s, 1H), 8.85 (s, 1H), 8.54 (d, J = 8.9 Hz, 1H), 8.49 (d,
J = 4.8 Hz, 1H), 8.34 (d, J = 9.3 Hz, 1H), 8.00 (d, J = 9.7 Hz, 1H), 7.75
525
Dyes and Pigments 160 (2019) 524–529
(d, J = 7.6 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.56 (t, J = 7.6 Hz, 1H),
6.75 (d, J = 9.7 Hz, 1H). FT-IR (KBr, cm−1): 3421, 3091, 2229, 1613,
1578, 1509, 1452, 1400, 1342, 1259, 1228, 1194, 1160, 1135, 1095,
1076. Anal. Calcd: C, 64.15; H, 3.17; N, 17.60%. Found: C, 63.65; H,
2.73; N, 17.67%.
Compound 4h: C16H9Cl2N3O3: HRMS, m/z: calcd for [M-H]-,
359.9948; found, 359.9935. 1H NMR (400 MHz, DMSO‑d6) δ (ppm):
15.66 (s, 1H), 8.50 (s, 2H), 8.35 (d, J = 8.1 Hz, 1H), 8.04 (d,
J = 9.6 Hz, 1H), 7.79 (d, J = 7.7 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.53
(t, J = 7.4 Hz, 1H), 6.83 (d, J = 9.6 Hz, 1H). FT-IR (KBr, cm−1): 3421,
3098, 1624, 1576, 1503, 1451, 1404, 1373, 1331, 1254, 1233, 1206,
1156, 1137, 1096, 1067. Anal. Calcd: C, 53.06; H, 2.50; N, 11.60%.
Found: C, 53.11; H, 2.26; N, 11.54%.
Compound 4i: C16H9Br2N3O3: HRMS, m/z: calcd for [M-H]-,
449.8917; found, 449.8903. 1H NMR (400 MHz, DMSO‑d6) δ (ppm):
15.25 (s, 1H), 8.64 (s, 2H), 8.48 (d, J = 8.1 Hz, 1H), 8.07 (d,
J = 9.5 Hz, 1H), 7.82 (d, J = 7.7 Hz, 1H), 7.64 (t, J = 7.7 Hz, 1H), 7.54
(t, J = 6.9 Hz, 1H), 6.92 (d, J = 9.5 Hz, 1H). FT-IR (KBr, cm−1): 3419,
3090, 1624, 1572, 1510, 1450, 1401, 1366, 1329, 1235, 1205, 1154,
1130, 1093, 1057. Anal. Calcd: C, 42.60; H, 2.01; N, 9.32%. Found: C,
42.71; H, 1.70; N, 9.48%.
Compound 4j: C16H10ClN3O3: HRMS, m/z: calcd for [M-H]-,
326.0338; found, 326.0326. 1H NMR (400 MHz, DMSO‑d6) δ (ppm):
16.07 (s, 1H), 8.51 (s, 1H), 8.48 (d, J = 8.1 Hz, 1H), 8.35 (d,
J = 3.2 Hz, 2H), 8.00 (d, J = 9.9 Hz, 1H), 7.75 (d, J = 7.7 Hz, 1H), 7.64
(t, J = 7.7 Hz, 1H), 7.59–7.50 (m, 1H), 6.73 (d, J = 9.7 Hz, 1H). FT-IR
(KBr, cm−1): 3420, 3099, 1623, 1574, 1587, 1555, 1509, 1452, 1403,
1338, 1261, 1231, 1201, 1158, 1132, 1094, 1041. Anal. Calcd: C,
58.64; H, 3.08; N, 12.82%. Found: C, 58.66; H, 2.69; N, 12.81%.
2.4. Post-treatment of dyestuff
0.5 g dye, 0.5 g dispersing agent NNO, 20 ml water and 95.0 g zir-
conia bead of 2.0 mm diameter were successively added in a 100 ml
glass grinding tube which installed with a glass grinding rod and a
mechanical agitator. The mixture was stirred for 1 h at room tempera-
ture with a rotate speed of 350 r/min and then filtrated through a 200
mesh sieve. The suspension solution was dried through a rotary eva-
poration at 60 °C, so the commercialized dye was obtained.
2.5. Dyeing for polyester fabric
Dyeing of polyester fabric was conducted using high temperature
high pressure method according to reference [7] in a rotary infrared
laboratory dyeing machine (XW-HWR-30-12, Jingjiang Xinwang
Dyeing & finishing Machinery factory, China). The fabric to liquor ratio
was all 1:100 and the amount of dye used was different according to K/
S. Take dye 4f as an example, the concentration of dye was 3% owf (on
weight of fabric) and the typical dyeing process is described as follows:
0.02 g commercialized dye of 4f was dissolved to 100 ml in a vo-
lumetric flask with water and the pH was adjusted to 5–6 using 10%
acetic acid solution. This dye liquor was poured into a 200 ml stainless
steel dyeing cylinder and then 1.0 g polyester fabric was also put in. The
dye bath temperature was raised from room temperature to 130 °C at a
rate of 3 °C/min, maintained at 130 °C for 60 min, and then naturally
cooled to 60 °C as depicted in Fig. 1. The dyed fabrics were rinsed with
water and then reduction cleared using an aqueous solution of 1.4 g/L
sodium hydroxide and 2.0 g/L sodium hydrosulfite at a fabric to liquor
ratio of 1:80 at 70 °C for 15 min. The treated fabrics were rinsed to
neutral with water and dried at ambient temperature.
2.6. Color measurement
The K/S, L*, a*, and b* values of the dyed fabrics were obtained
from an UltraScan XE spectrophotometer (Hunter Associates
Laboratory, Inc., USA) equipped with Universal Software V4.10 using
J. Qiu et al.
D65 illuminant at 10° observer.
2.7. Color fastness test
Color fastness tests were conducted according to international
standard: rubbing fastness used ISO 105-X12 (2001), washing fastness
used ISO 105-C10 (2006), light fastness used ISO 105-B02 (1994) and
sublimation fastness used ISO 105-P01 (1993). The change in tone of
fabrics and the fastness ratings were obtained by a non-contact digital
color measurement and imaging system, DigiEye (VeriVide Limited,
UK) under D65 illuminant.
3. Results and discussions
3.1. Synthesis of azo dyes
The coupling component was dissolved in an alkaline aqueous so-
lution, and the stable diazonium salt prepared freshly was added
slowly. During the addition of diazonium salts, the pH of the coupling
solution needed to be maintained within appropriate ranges according
to different coupling components: 10–11 in 2-naphthol solution and
9–10 in 1-phenyl-3-methyl-2-pyrazolin-5-one solution (Scheme 1). The
coupling was immediately completed once the adding of the reactant
was finished. The crude yields of the relevant azo dyes are from 79.4%
to 98.9%, and the purities are from 88.1% to 98.4%, which can be all
evaluated as good to excellent (Table 1). The structures of the dyes were
confirmed by HRMS, 1H NMR, FT-IR and elemental analysis (see Ex-
perimental section).
Coupling components with aromatic hydroxyl groups can be dis-
solved only in aqueous solutions with high pH. In addition, the
Scheme 1. Synthesis of disperse azo dyes from weakly basic amines and aromatic hydroxyl compounds.
526
Dyes and Pigments 160 (2019) 524–529
Fig. 1. Dyeing process for polyester fabrics with the
synthesized disperse azo dyes.
reactivity of such coupling compounds can be enhanced in high pH
solutions because of the formative negative ions of oxygen [28,29].
Nevertheless, in traditional methods, it is too hard for the diazonium
salts of weakly basic amines to react under this high pH condition be-
cause the diazotization is conducted in concentrated acid and a large
amount of inorganic salt and heat will be produced in the coupling
process. There is rare report about the synthesis of the dyes mentioned
in this article despite that the structures of the dyes are not compli-
cated. The diazonium salts of weakly basic amines in the present
method were obtained as stable solids which had separated from the
acidic diazotization solution, thus, the coupling reaction could be
conducted conveniently in alkaline aqueous solution. Moreover, the
reaction was rapid such that it was completed immediately after the
diazonium salts were added.
3.2. Spectral properties
Ultraviolet-visible absorption was measured in ethyl acetate. The
maximum absorption wavelength (λmax) and molar absorptivity (ε) are
summarized in Table 2. Dyes 4a-e are yellow and 4f-j are orange. The
change in λmax as the change of groups in dyes 4a-e or 4f-j complies
with the general rule [30]. Two commercial dyes, Y163 and O30, were
chosen as reference dyes and their structures are showed in Fig. 2. ε can
indicate the amount of dyes needed in dyeing and which is higher
signifies the lower dosage of the dyes. The ε values of the synthetic dyes
are all higher than 18,000 L mol-1∙cm-1, and most of them are similar to
or higher than the values of the two reference dyes (Table 2, entries 11,
12). The ε values of dyes 4b, 4c and 4e are even higher than
31,000 L mol-1∙cm-1 which are more outstanding than those of the se-
lected commercial dyes. Therefore, the relevant dyes in this study are
J. Qiu et al. Dyes and Pigments 160 (2019) 524–529

Table 1
The yields and purities of the synthetic azo dyes.
Entry Diazonium salt Coupling reagent product Structure number Crude yield (%) Purity (%)

1 2a 3a 4a 89.1 92.7

2 2b 3a 4b 79.4 98.4

3 2c 3a 4c 88.3 97.7

4 2d 3a 4d 90.7 95.5

5 2e 3a 4e 96.2 94.3

6 2a 3b 4f 95.8 93.5

7 2b 3b 4g 79.8 87.4

8 2c 3b 4h 88.4 91.8

9 2d 3b 4i 91.3 88.1

10 2e 3b 4j 98.9 89.2

Table 2 Table 3
UV-Vis data of ten synthetic azo dyes and two reference dyes in ethyl acetate. Parameters of dyeing and color values of the synthesized dyes and two re-
ference dyes.
Entry Dye λmax ε (L∙mol−1∙cm−1) Entry Dye λmax ε (L∙mol−1∙cm−1)
(nm) (nm) Entry Dye Concentration of Degree of K/S L* a* b*
dye (% owf) exhaustion
1 4a 403 26462 7 4g 473 18741 (%)
2 4b 390 31160 8 4h 471 18439
3 4c 381 31096 9 4i 469 24250 1 4a 2.0 75.4 3.5 84.59 4.25 41.56
4 4d 375 27677 10 4j 479 28808 2 4b 1.0 90.8 9.1 84.89 5.86 52.18
5 4e 400 35295 11 Y163 403 27671 3 4c 1.0 94.2 11.5 85.02 5.80 56.94
6 4f 473 25901 12 O30 411 25943 4 4d 2.0 75.2 11.5 81.07 6.25 57.27
5 4e 1.0 96.9 13.0 81.07 8.61 64.68
6 4f 3.0 79.1 5.1 71.73 37.15 57.01
suitable for dyeing. 7 4g 3.0 82.4 8.1 62.95 39.30 53.58
8 4h 2.0 89.1 16.2 61.80 48.07 66.91
9 4i 3.5 86.6 16.5 56.45 47.74 58.84
3.3. Dyeing and color assessment 10 4j 3.0 71.7 10.8 62.87 46.38 56.80
11 Y163 1.6 95.8 11.6 61.34 32.73 59.83
12 O30 3.4 85.8 17.6 51.12 41.01 54.14
Disperse dyes are insoluble in water. Products that are easily dis-
persed in water can be obtained in industry through grinding the dyes
by adding dispersants and then spray. We used a similar post-treatment Af ⎞
of synthetic dyes for producing commercialized dyes suitable for dyeing E (%) = ⎛1 −
⎜ × 100
⎟

(see Experimental section).
The concentrations of dyes were determined by the color apparent
depth that expressed by K/S values (Table 3), which can reach 1/1
standard depth used ISO-105-A01 (2010). There are five dyes reached
1/1 standard depth: 4c, 4d, 4e, 4h, and 4i (Table 3, entries 3–5, 9, and
10). That is to say these five dyes can be more suitable for dyeing deep
colors than the others. The concentrations of dyes 4a, 4b, 4f, 4g, and 4j
were determined by the maximum K/S (Table 3, entries 1, 2, 6, 7, and
10). The degree of exhaustion (E) was measured in ethanol-water (4:1,
v/v) and calculated according to Eq. (1).
⎝ A0 ⎠ (1)
where Af is the absorbance of the solution comprising residual liquids
from dyeing and reduction clearing, A0 is the absorbance of the initial
dyeing liquid with the same volume as the solution of the residual li-
quids. The E values of the ten dyes are all higher than 70% and those of
dyes 4b, 4c, and 4e are even higher than 90% (Table 3). Most of the
values are comparable with the E values of the two commercial dyes
(Table 3, entries 11, 12).
The color values are showed in Table 3 and it matches the spectral
data of the dyes. The a* values of dyes 4a-e are considerably smaller

Fig. 2. Structures of the two commercial dyes.

527
J. Qiu et al. Dyes and Pigments 160 (2019) 524–529

Table 4
Fastness properties of the synthesized dyes and two reference dyes.
Entry Dye Wash fastness Rubbing fastness Sublimation fastness Light fastness

Color change Polyester Cotton Dry Wet Color change Polyester Cotton

1 4a 4 4–5 4–5 4–5 4 4 4–5 4–5 6–7

2 4b 4 4–5 4–5 4–5 4–5 4 4 4–5 5–6
3 4c 4 4–5 4–5 5 5 3–4 3–4 4–5 6–7
4 4d 4 5 4–5 5 4–5 4 4 4–5 6–7
5 4e 4 4–5 4–5 4–5 4–5 4 3 4 5–6
6 4f 4 4–5 4–5 4 3–4 3–4 4 4–5 6–7
7 4g 3–4 4–5 4–5 4 3 3–4 3 4 5–6
8 4h 4–5 4–5 4–5 4–5 4–5 3 2 3 3–4
9 4i 4 5 4–5 4–5 4–5 3–4 2 3 3–4
10 4j 4 5 4–5 4 3 3–4 2–3 3–4 3–4
11 Y163 4–5 4–5 4–5 5 4–5 4–5 4–5 4–5 7–8
12 O30 5 4–5 4–5 5 4–5 4–5 3–4 4 6–7

than those of dyes 4f-j, suggesting that the color hue of dyes 4f-j tends
toward red more than dyes 4a-e. Therefore, dyes 4a-e are yellow and
dyes 4f-j are orange. Compared with the a* values of commercial dye
Y163, those of dyes 4a-e are considerably smaller, hence, the color hue
of dyes 4a-e tends to pure yellow more than that of Y163. Meanwhile,
the color hue of dyes 4f-j is similar to that of O30 because the color
values of them are similar. In addition, a comparison of 4c and Y163 or
4h and O30 in each color hue (These dyes have the same diazo com-
ponent.) show that the L* of dye 4c or 4h is higher than that of Y163 or
O30 when the K/S values are adjacent. In other words, the synthetic
dyes with aromatic hydroxyl group have a higher lightness than the
commercial dyes with conventional tertiary amines.
3.4. Fastness properties
Data about washing, rubbing, sublimation, and light fastnesses are
shown in Table 4. The synthetic dyes all demonstrate favorable washing
and rubbing fastness as all the ratings are above 4 except data few that
are approximately 3–4. Dyes 4a-g have moderate to excellent sub-
limation fastness and remarkable light fastness, which can be attributed
to the segments of the weakly basic amines in the dye structures as
traditional disperse azo dyes (Table 4, entries 11, 12). The sublimation
fastnesses of dyes 4h-j are only poor to moderate, especially the staining
ratings on polyester, which are only 2 or 2–3 (Table 4, entries 8–10).
Nevertheless, this may be an advantage as these three dyes can be
classed to ‘low energy’ disperse dyes, which have potential application
in transfer printing [31–33].
4. Conclusion
A novel synthetic strategy for the preparation of disperse azo dyes,
which was used weakly basic amines as diazo components and aromatic
hydroxyl compounds as coupling components at the same time, was
presented. This strategy solved the problem that the diazonium salts of
weakly basic amines could not be used under basic condition in tradi-
tional techniques by preventing the production of strong heat of dilu-
tion and neutralization and large amounts of waste mineral salt. A
series of disperse azo dyes containing aromatic hydroxyl group was
synthesized in good to excellent yields. The dyeing properties of these
synthetic dyes are comparable with those of commercial dyes and can
meet the actual demand of dyeing in the textile industry.
Acknowledgments
This work was sponsored by the National Natural Science
Foundation of China, China (NO. 21421005 and 21576039);
Fundamental Research Funds for the Central Universities, China
(DUT18ZD218).
References
[1] Zakerhamidi MS, Keshavarz M, Tajalli H, Ghanadzadeh A, Ahmadi S, Moghadam M,
et al. Isotropic and anisotropic environment effects on the UV/vis absorption spectra
of three disperse azo dyes. J Mol Liq 2010;154:94–101.
[2] Valizadeh H, Shomali A, Nourshargh S, Mohammad-Rezaei R. Carboxyl and nitrite
functionalized graphene quantum dots as a highly active reagent and catalyst for
rapid diazotization reaction and synthesis of azo-dyes under solvent-free conditions.
Dyes Pigments 2015;113:522–8.
[3] Gharanjig K, Arami M, Bahrami H, Movassagh B, Mahmoodi NM, Rouhani S.
Synthesis, spectral properties and application of novel monoazo disperse dyes de-
rived from N-ester-1,8-naphthalimide to polyester. Dyes Pigments 2008;76:684–9.
[4] Yazdanbakhsh MR, Mohammadi A, Mohajerani E, Nemati H, Nataj NH, Moheghi A,
et al. Novel azo disperse dyes derived from N-benzyl-N-ethyl-aniline: synthesis,
solvatochromic and optical properties. J Mol Liq 2010;151:107–12.
[5] Shan B, Tong X, Xiong W, Qiu WZ, Tang BT, Lu RW, et al. A new kind of H-acid
monoazo-anthraquinone reactive dyes with surprising colour. Dyes Pigments
2015;123:44–54.
[6] Satam MA, Raut RK, Telore RD, Sekar N. Fluorescent acid azo dyes from 3-(1,3-
benzothiazol-2-yl)naphthalen-2-ol and comparison with 2-naphthol analogs. Dyes
Pigments 2013;97:32–42.
[7] Deshmukh MS, Sekar N. A combined experimental and TD-DFT investigation of
three disperse azo dyes having the nitroterephthalate skeleton. Dyes Pigments
2014;103:25–33.
[8] Satam MA, Raut RK, Sekar N. Fluorescent azo disperse dyes from 3-(1,3-ben-
zothiazol-2-yl)naphthalen-2-ol and comparison with 2-naphthol analogs. Dyes
Pigments 2013;96:92–103.
[9] Raditoiu V, Raditoiu A, Wagner L, Amariutei V, Raduly M, Nicolae CA. Disperse
dyes functionalized with trialkoxysilane groups. Rev Chim (Bucharest)
2011;62:409–14.
[10] Nowack P, Lauk U, Tzikas A, Inventor; huntsman international LLC, assignee.
Disperse azo dyes. United states patent US 20130255011. 2013 Oct 2.
[11] Wagner L, Raditoiu V, Raditoiu A, Ardeleanu P, Amariutei V, Raduly M.
Functionalized azobenzenes chromogens with aromatic amino primary groups. Rev
Chim (Bucharest) 2009;60:444–9.
[12] Nicolescu FA, Jerca VV, Draghici C, Vuluga DM, Vasilescu DS. Synthesis and
characterization of novel azobenzene methacrylate monomers. Des Monomers
Polym 2009;12:553–63.
[13] Sun J, Zheng CL, Tuncer H. X-ray crystal structure analysis for CI Disperse Orange
61. Color Technol 2012;128:91–4.
[14] Odintsova OI, Krotova MN, Mel'nikov BN. Use of cationic agents for fixing colora-
tion of textile materials. Russ J Appl Chem 2009;82:461–5.
[15] Yang CX, Li YF, Huang CZ. Determination of total protein content in human serum
samples with fast red VR by resonance light scattering technique. Anal Lett
2002;35:1945–57.
[16] Hihara T, Okada Y, Morita Z. Azo-hydrazone tautomerism of phenylazonaphthol
sulfonates and their analysis using the semiempirical molecular orbital PM5
method. Dyes Pigments 2003;59:25–41.
[17] Weisz A, Ridge CD, Mazzola EP, Ito Y. Preparative separation and identification of
novel subsidiary colors of the color additive D&C Red No. 33 (Acid Red 33) using
spiral high-speed counter-current chromatography. J Chromatogr A
2015;1380:120–9.
[18] Wang HQ, Li Z, Niu Q, Ma JT, Jia Q. Preparation of a zeolite-modified polymer
monolith for identification of synthetic colorants in lipsticks. Appl Surf Sci
2015;353:1326–33.
[19] Lv JG, Liu S, Feng JM, LiuY, Zhou SD, Chen R. Effective identification of paints
pigments in hit-and-run cases with confocal Raman microscope. Pigment Resin
Technol 2016;45:294–300.
[20] Mkpenie VN, Essien EE. Solvent and methyl group effects on the electronic spectral
properties of azo-2-naphthol dye. Am Chem Sci J 2015;8:1–8.
[21] Mansouri L, Zouchoune B. Substitution effects and electronic properties of the azo
dye (1-phenylazo-2-naphthol) species: a TD-DFT electronic spectra investigation.
Can J Chem 2014;93:509–17.

528
J. Qiu et al.
[22] Lin ST, Lin LH, Lin YC, Ding MF. Substituent effect on the tautomerization of 1-
arylazonaphthalen-2-ols by mass spectrometric analysis. J Chin Chem Soc
2015;62:257–62.
[23] Hihara T, Okada Y, Morita Z. A semiempirical molecular orbital study of the photo-
reactivity of monoazo reactive dyes derived from γ- and J-acids. Dyes pigment
2007;73:141–61.
[24] Koukabi N, Otokesh S, Kolvari E, Amoozadeh A. Convenient and rapid diazotization
and diazo coupling reaction via aryl diazonium nanomagnetic sulfate under solvent-
free conditions at room temperature. Dyes Pigments 2016;124:12–7.
[25] Papee HM, Canady WJ, Laidler KJ. The heat of neutralization of strong acids and
bases in highly dilute aqueous solutions. Can J Chem 1956;34:1677–82.
[26] Pitzer KS. The heats of ionization of water, ammonium hydroxide, carbonic,
phosphoric, and sulfuric acids. The variation of ionization constants with tem-
perature and the entropy change with ionization. J Am Chem Soc
1937;59:2365–71.
529
Dyes and Pigments 160 (2019) 524–529
[27] Qiu JJ, Tang BT, Ju BZ, Xu YJ, Zhang SF. Stable diazonium salts of weakly basic
amines—convenient reagents for synthesis of disperse azo dyes. Dyes Pigments
2017;136:63–9.
[28] Nachlas MM, Goldstein TP, Rosenblatt DH, Kirsch M, Seligman AM. Influence of
chemical structure on the rate of azo coupling and its significance in histochemical
methodology. J Histochem Cytochem 1959;7:50–66.
[29] Zollinger H. The kinetics of the diazo coupling reaction. Chem Rev 1952;51:347–61.
[30] Kim SD, Park EJ. Relation between chemical structure of yellow disperse dyes and
their lightfastness. Fibers Polym 2001;2:159–63.
[31] Dawson JF. The structure and properties of disperse dyes in polyester coloration.
Color Technol 1983;99:183–91.
[32] Donenfeld H, inventor; Doncroft Colors & Chemicals Inc., assignee. Sublimation dye
transfer printing of fabrics: United States Patent 4576610. 1986 Mar 18.
[33] Hale N, Xu M, inventor; Sawgrass Systems Inc., assignee. Low energy heat activated
transfer printing process. United States Patent US 5640180. 1997 Jun 17.