Accepted Manuscript

Synthesis of a nitrite functionalized star-like poly ionic compound as a highly efficient

nitrosonium source and catalyst for the diazotization of anilines and subsequent facile
synthesis of azo dyes under solvent-free conditions

Hassan Valizadeh, Ashkan Shomali, Jalal Ghorbani, Saeideh Noorshargh

PII: S0143-7208(15)00043-1
DOI: 10.1016/j.dyepig.2015.02.007
Reference: DYPI 4661

To appear in: Dyes and Pigments

Received Date: 20 December 2014

Revised Date: 6 February 2015
Accepted Date: 9 February 2015

Please cite this article as: Valizadeh H, Shomali A, Ghorbani J, Noorshargh S, Synthesis of a nitrite
functionalized star-like poly ionic compound as a highly efficient nitrosonium source and catalyst for the
diazotization of anilines and subsequent facile synthesis of azo dyes under solvent-free conditions, Dyes
and Pigments (2015), doi: 10.1016/j.dyepig.2015.02.007.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

Synthesis of a nitrite functionalized star-like poly ionic compound as a highly

efficient nitrosonium source and catalyst for the diazotization of anilines and

subsequent facile synthesis of azo dyes under solvent-free conditions

PT
Hassan Valizadeh∗, Ashkan Shomali, Jalal Ghorbani, Saeideh Noorshargh

RI
Department of Chemistry, Faculty of Sciences, Azarbaijan Shahid Madani University, Tabriz, Iran.

U SC
AN
M
D
TE
C EP
AC

∗
Corresponding author: Tel: +98-41-33856447, Fax: +98-41-34327541; P.O. Box 53714-161; E-mail address:
hvalizadeh2@yahoo.com

1
 ACCEPTED MANUSCRIPT

Abstract

PT
Nitrite functionalized star-like poly ionic (NFSPI) compound was synthesized and used as a

RI
highly efficient nitrosonium source and catalyst for the conversion of aniline derivatives to

diazonium salts. Azo dyes were prepared via in situ azo-coupling reaction of these diazoniums

SC
with active aromatic compounds under solvent-free conditions in very short reaction time in

U
excellent yields. NFSPI plays dual role as a three-dimensional nitrosonium source and catalyst
AN
because of its poly ionic characteristic. The isolated products were confirmed with FT-IR
1 13
spectrum, H-NMR, C-NMR spectroscopy and CHNSO analysis. The structure of
M

heterogeneous reagent and catalyst was confirmed by FT-IR spectrum, SEM images, EDX and

CHNSO analysis. Yields and reaction times for the synthesis of a variety of products via this
D

procedure were compared with reported values in literature.

TE
EP

Keyword: Azo dyes; diazonium salts; heterogeneous catalyst; nitrite functionalized poly ionic,

solvent-free; star-like.
C
AC

2
 ACCEPTED MANUSCRIPT

1. Introduction

Aromatic azo compounds are very important chemical materials because of their widely

applications in industry as dyes and pigments [1], therapeutic agents [2] and drug deliveries [3].

PT
Diazonium salts have been frequently used for the preparation of synthetic azo dyes [4]. Many

reports have been published for diazotization and also for azo-coupling reactions in literature [5-

RI
7]. However, many of these reported methods suffer from one or more practical drawbacks

associated with hazardous reagents, long reaction times, less effective catalysts, formation of

SC
side products and difficult and time consumed work-up procedure. To eliminate of some of these

U
explained limitations, in the present research we utilize a poly ionic heterogonous nitrosonium
AN
source which plays the dual role as reagent and catalyst. The easy work-up procedure, very short

reaction times and also high yields of the products were achieved by using of this reagent.
M

Having the unique behavior of organic-inorganic composites, there are a lot of interests in

developing of the synthesis and applications of new structures of these compounds [8]. Recently,
D

a lot of attentions have been paid to the construction of three-dimensional molecules such as star-
TE

like polymers due to their importance in drug-delivery [9], catalysis [10], etc. Liu et al. have
EP

been reported the preparation of a three-dimensional star-like polymer that was prepared via

connection of linear polymers to a central reactive core [11]. The most of reported star-like
C

polymers are on the base of organic materials which are unstable, toxic, and non-ionic
AC

compounds [12]. According to the some interesting characteristics of ionic liquids, synthesis of

three-dimensional star-like compounds based on ionic liquids could play an important role in

synthetic organic chemistry. In continuation of our work on the using of nitrite ionic liquid

immobilized on silica for the diazotization of aniline derivatives [13], herein we introduced a

new rapid and efficient method for this reaction and subsequent synthesis of azo dyes. In this

3
 ACCEPTED MANUSCRIPT

study, NFSPI compound was used as a new nitrosonium source and catalyst for the efficient

diazotization of aniline derivatives and synthesis of azo dyes under solvent free conditions

(Scheme 1).

PT
<<Scheme 1>>

RI
2. Experimental

2.1. Materials and instrumentation

SC
All reagents purchased from Merck Company and used without further purification. Infrared

spectra were recorded in KBr and determined on a Perkin Elmer FT-IR spectrometer. 1HNMR

and 13

U
CNMR spectra were recorded on a Bruker Avance AC-400 MHz using DMSO-d6 or
AN
CDCl3 as the deuterated solvent and TMS as internal standard. All melting point measured in
M

open glass-capillaries using a Stuart melting point apparatus. The morphology of the catalyst was

studied by field emission scanning electron microscopy using FESEM; Hitachi, model S-4160.
D

Structure of catalyst was confirmed by energy–dispersive X-ray analysis using EDX; Tescan;
TE

model MIRA3FEG-SEM and elemental analysis was determined by CHNSO; Euro EA; model

EA3000.
EP

2.2. Synthesis of silica nanoparticles

C

Ammonia solution 25% (750 µL, 10 mmol) and water (1.98 mL) were poured in a 250 mL round
AC

bottom flask containing absolute methanol (100 mL). While stirring of the solution,

tetraethoxysilane, TEOS (11 ml, 50 mmol) was added slowly. The solution was stirred for three

days at ambient temperature. The silica nano particles was isolated and confirmed by scanning

electron microscopy image. FT-IR (KBr, cm-1): 3456 (Si-OH), 1639 (O-H), 1097 and 803 (Si-O).

4
 ACCEPTED MANUSCRIPT

2.3. Synthesis of star-like poly ionic compound 8:

N,N,N',N'-Tetramethylethylenediamine (11 mmol) was added to a round bottom flask containing

acetonitrile (10 mL). While stirring, (3-chloropropyl)trimethoxysilane (10 mmol) was poured

into the solution dropwise. Then, the solution was stirred for three days at 80ºC to produce ionic

PT
liquid 6. The unreacted materials were washed by acetonitrile. The resulted ionic liquid 6 and

RI
silica nanoparticles were refluxed in acetonitrile for three days at 60ºC. The acetonitrile was

removed under reduced pressure at 40ºC to produce crude product 7. Isolated yield was 90%. FT-

SC
IR (KBr, cm-1): 3451 (Si-OH), 2956 (C-H), 1637, 1486 (C-H), 1090 (SiO-H), 800 (Si-O). EDX:

U
Calcd. (%w): N/C= 0.259; Found (%): C, 16.93; N, 4.37; H, 3.92; %w N/C= 0.258. CHNSO:
AN
Calcd. (%w): N/C= 0.259; Found (%): C, 16.93; N, 4.37; H, 3.92; N/C= 0.258. Then, 1,4-

dichlorobutane (10 mmol) and product 7 were added to acetonitrile (15 mL) and mixed
M

thoroughly. The mixture was refluxed at 80ºC for three days. Then the mixture was poured in

acetonitrile and stirred thoroughly and unreacted regents were removed by centrifuging. After
D

this, the product was reacted with diamine and then with 1,4-dichlorobutane under the above
TE

described conditions to produce the product 8. The morphology and structure of the product was

confirmed and identified by scanning electron microscopy FE-SEM, FT-IR spectroscopy, EDX,
EP

and CHNSO analysis. FT-IR (KBr, cm-1): 3442 (Si-OH), 2958 (C-H), 1638, 1486 (C-H), 1093

(SiO-H), 800 (Si-O). EDX: Calcd. (%w): N/C= 0.246. CHNSO: Calcd. N/C (%w) = 0.241;
C
AC

Found (%): C, 17.76; N, 4.37; H, 4.24, N/C= 0.246

2.4. Synthesis of hydroxyl functionalized star-like poly ionic compound 9:

4-Chlorobutanol (10 mmol) was added into a solution of compound 8 in acetonitrile while

stirring and the mixture was refluxed for three days at 80ºC. Hydroxyl functionalized star–like

5
 ACCEPTED MANUSCRIPT

poly ionic product 9 was isolated as the same work-up procedure which described for the

compound 8. The structure of product was confirmed by comparison of FT-IR spectroscopy of

compounds 8 and 9 (Figure 2, B). FT-IR (KBr, cm-1): 3420 (O-H), 2958 (C-H), 1636 (O-H),

1482 (C-H), 1402 (bending O-H), 1087 (Si-O), 951 (Si-OH), 801 (Si-O).

PT
2.5. Synthesis of NFSPI compound 10:

RI
Freshly prepared compound 9 (10 g) was added to an aqueous solution of sodium nitrite (15 ml).

SC
HCl (37%, 3 mL) was added slowly to the mixture while stirring at 0-5ºC. The mixture was

filtered off and washed with cold water (20 mL) and the crude product 10 was dried under

U
vacuum at room temperature. Functional group conversion was confirmed by comparison of the
AN
FT-IR spectra of compounds 9 and 10 (Figure 2, B). FT-IR (KBr, cm-1): 3440 (SiO-H), 2958 (C-

H), 1637 (O-H), 1483 (C-H), 1384 (N=O), 1090 (Si-O), 952 (Si-OH), 801 (Si-O).
M

2.6. General procedure for the synthesis of azo dyes 3a-t

D
TE

Aniline derivative was added to a vessel containing HCl 37% (0.5 ml) and the mixture was

stirred in ice bath at 0-5 ºC. Then, NFSPI 10 was added to the mixture and grinded at room
EP

temperature for the times shown in Table 2 to produce the related diazonium salt. The phenolate

compound was added slowly to the mixture to produce the desired azo dye at 0-5ºC. After
C

completion of the reaction, ethyl acetate was added to the reaction mixture and stirred
AC

thoroughly. Then, poly ionic compound 9 was filtered off and the crude azo dye was isolated by

evaporation of ethyl acetate. For more purification, crude product was recrystallized from

ethanol/H2O. The products were characterized by their FT-IR, 1H-NMR and 13C-NMR spectra.

2.7. Spectroscopic and analytical data

6
 ACCEPTED MANUSCRIPT

2.7.1. 4-(3-Nitrophenylazo) phenol (3a)

C12H9N3O3 [14]: FT-IR (KBr, cm-1): 3416, 1623, 1591, 1338, 730. 1H NMR (400 MHz, DMSO-

d6) δ (ppm): 8.78 (s, 1H); 8.36 (1H, d, J = 5.2 Hz); 8.20 (1H, d, J = 5.4 Hz); 7.92 (1H, m), 7.84

PT
(2H. d, J = 8.1 Hz); 7.01 (2H, d, J = 8.1 Hz); 5.34 (1H, s-br); 13C NMR (100 MHz, DMSO-d6) δ

(ppm): 154.0, 152.5, 149.5, 129.2, 128.8, 128.3, 128.0, 124.3, 124.0, 123.1, 122.7. Anal. Calc.

RI
for C12H9N3O3: C, 59.26; H, 3.70; N, 17.28%. Found: C, 59.27; H, 3.72; N, 17.25%.

SC
2.7.2. 4-(4-Bromophenylazo) phenol (3b)

C12H9N2BrO [14]: FT-IR (KBr, cm-1): 3399, 1627, 713, 533. 1H NMR (400 MHz, DMSO-d6) δ

U
(ppm): 7.80 (1H, d, J = 8.1 Hz); 7.74 (2H, m); 7.66 (2H, m); 7.57 (1H, m); 7.39 (1H, m); 6.95
AN
13
(1H, m); C NMR (100 MHz, DMSO-d6) δ (ppm): 153.3, 151.5, 133.3, 132.5, 132.1, 130.7,
M

127.3, 124.0, 123.1, 122.7, 122.1, 115.7. Anal. Calc. for C12H9N2BrO: C, 51.98; H, 3.25; N,

10.11%. Found: C, 51.96; H, 3.29; N, 10.10%.

D

2.7.3. 4-(4-Chlorophenylazo) phenol (3c)

TE

C12H9N2ClO [14]: FT-IR (KBr, cm-1): 3400, 1556, 839, 719. 1H NMR (400 MHz, DMSO-d6) δ
EP

(ppm): 8.01 (1H, d, J = 4.3 Hz); 7.81(2H, m); 7.73 (1H, d, J = 8.2 Hz); 7.60 (1H, d, J = 8.2 Hz);

7.54 (2H, m); 6.96 (1H, d, J = 8.2 Hz); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 153.6, 153.1,
C

133.2, 133.1, 132.7, 131.5, 127.0, 125.8, 124.9, 123.2, 123.7, 116.4. Anal. Calc. for
AC

C12H9N2ClO: C, 61.93; H, 3.87; N, 12.04%. Found: C, 61.99; H, 3.80; N, 12.09%.

2.7.4. 4-Phenylazophenol (3d)

C12H10N2O [14]: FT-IR (KBr, cm-1): 3190, 1579, 720. 1H NMR (400 MHz, DMSO-d6) δ (ppm):

8.26-8.21 (2H, d, J = 10.4 Hz); 7.83 (2H, d, J = 8.1 Hz); 7.66 (2H, t, J = 10.4 Hz); 7.28 (1H, t, J

7
 ACCEPTED MANUSCRIPT

= 10.4 Hz); 7.01 (2H, d, J = 8.1 Hz); 5.31 (1H, s-br); 13C NMR (100 MHz, DMSO-d6) δ (ppm):

161.3, 152.8, 146.3, 131.8, 129.1, 125.5, 124.7, 122.0, 116.4, 116.1. Anal. Calc. for C12H10N2O:

C, 72.73; H, 5.05; N, 14.14%. Found: C, 72.68; H, 5.11; N, 14.12%.

PT
2.7.5. 4-((3-Bromo-4-methyl)phenylazo) phenol (3e)

C12H11N2BrO [14]: FT-IR (KBr, cm-1): 3298, 1579, 721, 572. 1H NMR (400 MHz, DMSO-d6) δ

RI
(ppm): 7.82 (2H, d, J = 8.2 Hz); 7.73 (1H, s); 7.53(1H, d, J = 8.2 Hz); 7.30 (1H, d, J = 8.2 Hz);

SC
7.04 (2H, dd, J1 = 4.1 Hz, J2 = 12.4 Hz); 2.37 (3H, s); 13C NMR (100 MHz, DMSO-d6) δ (ppm):

146.3, 145.8, 143.2, 131.5, 128.2, 124.2, 125.2, 124.1, 118.1, 116.8, 115.3, 21.9. Anal. Calc. for

U
C12H11N2BrO: C, 53.61; H, 3.78; N, 9.62%. Found: C, 53.67; H, 3.81; N, 9.66%.
AN
2.7.6. 4-(4-Nitrophenylazo) resorcinol (3f)
M

C12H9N3O4 [5]: FT-IR (KBr, cm-1): 3440 (bs), 3366, 1619, 1610. 1H NMR (400 MHz, CDCl3) δ

(ppm): 12.23 (OH, s); 8.83 (OH, s); 7.75 (2H, d, J = 8.19 Hz); 7.83 (2H, d, J = 8.19 Hz); 7.74
D

(1H, d, J = 8.12 Hz); 6.62 (1H, dd, J = 8.12 and 2.48 Hz); 6.32 (1H, d, J = 2.48 Hz,); 13C NMR
TE

(100 MHz, CDCl3) δ (ppm): 156.22, 148.73, 148.12, 145.16, 131.41, 128.35, 127.38, 121.31,

111.69, 104.18. Anal. Calc. for C12H9N3O4: C, 55.59; H, 3.47; N, 16.21%. Found: C, 55.62; H,
EP

3.51; N, 16.28%.
C

2.7.7. 2-Nitro-4-(4-chlorophenylazo) phenol (3g)

AC

C12H8N3ClO3 [15]: FT-IR (KBr, cm-1): 3432, 1623, 1510, 1120. 1H NMR (400 MHz, DMSO-d6)
13
δ (ppm): 12.67 (OH, s); 8.33 (1H, s); 7.71 (2H, d, J = 8.3 Hz); 7.43 (4H, m); C NMR (100

MHz, DMSO-d6) δ (ppm): 168.21, 150.47, 138.53, 137.71, 132.71, 128.40, 128.04, 124.55,

122.43, 115.47. Anal. Calc. for C12H8N3ClO3: C, 51.89; H, 2.88; N, 15.13%. Found: C, 51.92; H,

2.79; N, 15.19%.
8
 ACCEPTED MANUSCRIPT

2.7.8. 2-Nitro-4-(4-methylphenylazo) phenol (3h)

C13H11N3O3 [15]: FT-IR (KBr, cm-1): 3459, 2970, 1629, 1480, 1133. 1H NMR (400 MHz,
13
DMSO-d6) δ (ppm): 8.40-6.7 (7H, m); 2.17 (3H, s); C NMR (100 MHz, DMSO-d6) δ (ppm):

PT
143.15, 132.27, 130.81, 130.41, 130.23, 130.03, 128.76, 128.34, 124.66, 121.80, 120.86, 120.28,

116.67. Anal. Calc. for C13H11N3O3: C, 60.70; H, 4.28; N, 16.34%. Found: C, 60.68; H, 4.31; N,

RI
16.28%.

SC
2.7.9. 1-(4-Methylphenylazo)-2-naphthol (3i)

C17H14N2O [15]: FT-IR (KBr, cm-1): 3419, 2940, 1627, 1489, 1344. 1H NMR (400 MHz,

U
DMSO-d6) δ (ppm): 15.29 (1H, s); 8.39 (1H, d, J = 8.2 Hz); 7.91 (1H, d, J = 9.1 Hz); 7.80 (3H,
AN
m); 7.66 (1H, t, J = 8.2 Hz); 7.32 (1H, t, J = 7.2 Hz); 7.21 (2H, d, J = 8.2 Hz); 6.79 (1H, d, J =
13
C NMR (100 MHz, CDCl3) δ (ppm): 164.1, 144.51, 140.21, 139.19,
M

9.1 Hz); 2.26 (3H, s);

130.46, 129.71, 128.23, 126.72, 126.36, 123.33, 122.61, 121.19, 20.32. Anal. Calc. for
D

C17H14N2O: C, 77.86; H, 5.34; N, 10.69%. Found: C, 77.83; H, 5.38; N, 10.71%.

TE

2.7.10. 1-(4-Bromophenylazo)-2-naphthol (3j)

EP

C16H11N2BrO [14]: FT-IR (KBr, cm-1): 3415, 1611, 729, 522. 1H NMR (400 MHz, DMSO-d6) δ

(ppm): 8.55 (1H, d, J = 8.2 Hz); 8.11 (1H, d, J = 1.6 Hz); 7.96 (1H, d, J = 9.4 Hz); 7.80 (2H, d, J
C

= 8.2 Hz); 7.62 (2H, t, J = 8.2 Hz); 7.51 (1H, d, J = 10.1 Hz); 7.45 (1H, d, J = 10.1 Hz); 6.965
AC

13
(1H, d, J = 9.4 Hz); C NMR (100 MHz, CDCl3) δ (ppm): 148.6, 148.1, 147.6, 138.2, 135.2,

132.7, 132.5, 130.9, 130.3, 130.1, 129.4, 129.1, 128.8, 127.7, 126.1, 125.9. Anal. Calc. for

C16H11N2BrO: C, 58.71; H, 3.36; N, 8.56%. Found: C, 58.73; H, 3.39; N, 8.51%.

2.7.11. 1-(3-Nitrophenylazo)-2-naphthol (3k)

9
 ACCEPTED MANUSCRIPT

C16H11N3O3 [14]: FT-IR (KBr, cm-1): 3378, 1624, 1512, 1332, 718. 1H NMR (400 MHz, DMSO-

d6) δ (ppm): 8.53 (1H, s); 8.51 (1H, d, J = 8.3 Hz); 8.21 (1H, d, J = 8.3 Hz); 8.03 (2H, d, J = 8.3

Hz); 7.86 (1H, t, J = 9.8 Hz); 7.71 (2H, t, J = 8.3 Hz); 7.64 (1H, d, J = 8.3 Hz); 7.50 (1H, t, J =

7.5 Hz); 7.21 (1H, t, J = 7.4 Hz); 6.75 (1H, d, J = 8.3 Hz); 13C NMR (100 MHz, CDCl3) δ: 134.6,

PT
130.3, 130.2, 129.9, 128.4, 128.4, 128.1, 127.7, 126.4, 125.9, 123.9, 123.5, 121.5, 121.3, 119.3,

RI
118.7. Anal. Calc. for C16H11N3O3: C, 65.53; H, 3.75; N, 14.33%. Found: C, 65.57; H, 3.79; N,

14.39%.

SC
2.7.12. 1-(4-Nitrophenylazo)-2-naphthol (3l)

U
C16H11N3O3 [5]: FT-IR (KBr, cm-1): 3411 (bs), 1650, 1613. 1H NMR (400 MHz, CDCl3) δ
AN
(ppm): 12.16 (OH, s), 8.58 (1H, dd, J = 8.13 and 2.03 Hz); 7.85 (2H, d, J = 7.88 Hz); 7.68 (2H,

d, J = 7.88); 7.51 (1H, d, J = 7.28 Hz); 7.49 (1H, d, J = 7.28 Hz); 7.45 (1H, dd, J = 7.95 and 2.02
M

13
Hz); 7.43 (1H, dt, J = 7.65 and 1.99 Hz); 7.42 (1H, dt, J = 7.75 and 1.97 Hz); C NMR (100
D

MHz, CDCl3) δ (ppm): 143.33, 137.30, 134.15, 131.15, 128.47, 127.87, 124.12, 121.33, 120.13,
TE

119.35, 119.23, 117.14, 115.71, 111.18. Anal. Calc. for C16H11N3O3: C, 65.53; H, 3.75; N,

14.33%. Found: C, 65.54; H, 3.72; N, 14.41%.

EP

2.7.13. 1-(4-Chlorophenylazo)-2-naphthol (3m)

C16H11N2ClO [14]: FT-IR (KBr, cm-1): 3330, 1628, 829, 720. 1H NMR (400 MHz, DMSO-d6) δ
C
AC

(ppm): 8.54 (1H, d, J = 8.1 Hz); 8.15 (1H, d, J = 12.0 Hz); 7.94 (1H, d, J = 9.4 Hz); 7.84 (2H, d,

J = 8.1 Hz); 7.62 (2H, t, J = 8.1 Hz); 7.50 (1H, d, J = 10.0 Hz); 7.43 (1H, d, J = 10.0 Hz); 6.95
13
(1H, d, J = 9.4 Hz); C NMR (100 MHz, CDCl3) δ (ppm): 149.7, 148.2, 147.6, 138.5, 134.1,

132.4, 132.1, 130.6, 130.4, 130.1, 128.4, 128.2, 127.7, 127.5, 126.1, 124.3. Anal. Calc. for

C16H11N2ClO: C, 67.96; H, 3.89; N, 9.91%. Found: C, 67.99; H, 3.92; N, 9.95%.

10
 ACCEPTED MANUSCRIPT

2.7.14. N,N-dimethyl-4-(phenylazo) aniline (3n)

C14H15N3 [15]: FT-IR (KBr, cm-1): 1618, 1524, 1518, 1460. 1H NMR (400 MHz, CDCl3) δ
13
(ppm): 77.63 (2H, d, J = 7.89 Hz); 7.36 (5H, m); 6.76 (2H, d, J = 7.89 Hz); 3.58 (6H, s); C

PT
NMR (100 MHz, CDCl3) δ (ppm): 134.52, 128.73, 126.43, 125.45, 123.31, 120.27, 117.46,

114.41, 35.52. Anal. Calc. for C14H15N3: C, 74.66; H, 6.67; N, 18.67%. Found: C, 74.65; H,

RI
6.69; N, 18.64%.

SC
2.7.15. N,N-dimethyl-4-(4-nitrophenylazo) aniline (3o)

C14H14N4O2 [16]: FT-IR (KBr, cm-1): 1617, 1511, 1469, 1546, 1332. 1H NMR (400 MHz,

U
CDCl3) δ (ppm): 7.73 (2H, d, J = 8.12 Hz); 7.70 (2H, d, J = 8.12); 7.66 (2H, d, J = 7.96 Hz);
AN
6.69 (2H, d, J = 7.96 Hz); 3.51 (6H, s); 13C NMR (100 MHz, CDCl3) δ (ppm): 156.43, 135.58,
M

128.43, 126.59, 125.34, 122.43, 121.17, 117.84, 116.21, 34.32. Anal. Calc. for C14H14N4O2: C,

62.22; H, 5.18; N, 20.74%. Found: C, 62.27; H, 5.21; N, 20.71%.

D

2.7.16. N,N-dimethyl-4-(2-chloro-4-nitrophenylazo) aniline (3p)

TE

C14H13N4ClO2 [16]: FT-IR (KBr, cm-1): 1631, 1520, 1471, 1539, 1329.1H NMR (400 MHz,
EP

CDCl3) δ (ppm): 8.33 (1H, dd, J = 2.5 and 0.4 Hz); 8.14 (1H, dd, J = 9.0 and 2.4 Hz,); 7.99 (2H,

m); 7.79 (1H, d, J = 8.9 Hz); 6.82 (2H, m); 3.16 (6H, s); 13C NMR (125 MHz, CDCl3) δ (ppm):
C

153.1, 152.0, 147.9, 143.4, 133.0, 128.9, 126.9, 123.6, 117.1, 112.8, 41.6. Anal. Calc. for
AC

C14H13N4ClO2: C, 55.17; H, 4.27; N, 18.39%. Found: C, 55.19; H, 4.26; N, 18.41%.

2.7.17. 3-Formyl-2-(2-carboxylicacidphenylazo)1H-indol (3q)

C16H11N3O3 [17]: FT-IR (KBr, cm-1): 3412, 3100, 1650, 1537, 1350; 1H NMR (400 MHz,

CDCl3) δ (ppm): 11.91 (1H, s); 11.15 (1H, s); 9.75 (1H, s); 8.27 (2H, d, J = 7.69 Hz); 7.91 (d, J

11
 ACCEPTED MANUSCRIPT

13
= 7.47 Hz, 2H); 7.79 (2H, m); 7.47 (2H, m); C NMR (100 MHz, CDCl3) δ (ppm): 164.25,

161.13, 134.32, 131.28, 130.83, 128.47, 127.91, 125.73, 125.62, 124.49, 124.06, 123.33, 121.52,

120.21, 116.79, 115.42. Anal. Calc. for C16H11N3O3: C, 65.53; H, 3.75; N, 14.33%. Found: C,

65.51; H, 3.73; N, 14.31%.

PT
2.7.18. 3-Formyl-2-(phenylazo)1H-indol (3r)

RI
C15H11N3O [17]: FT-IR (KBr, cm-1): 1785, 1624, 1533, 1122; 1H NMR (400 MHz, CDCl3) δ

SC
(ppm): 11.89 (1H, s); 9.82 (1H, s); 8.22 (1H, dd, J = 7.59 and 2.08 Hz); 7.31 (1H, dd, J = 7.43

and 2.04 Hz); 7.55 (2H, m); 7.21 (2H, m); 7.03 (3H, m); 13C NMR (100 MHz, CDCl3) δ (ppm):

U
162.54, 131.44, 130.72, 125.96, 124.45, 123.13, 122.64, 122.13, 121.25, 121.02, 117.42, 115.15,
AN
112.74. Anal. Calc. for C15H11N3O: C, 72.29; H, 4.42; N, 16.87%. Found: C, 72.28; H, 4.39; N,

16.84%.
M

2.7.19. 2-(4-Chlorophenylazo) naphthol (3s)

D

C16H11N2ClO [18]: FT-IR (KBr, cm-1): 3418 (bs), 3012, 1629, 1471, 1428, 1218, 812, 738. 1H
TE

NMR (400 MHz, CDCl3) δ (ppm): 16.42 (1H, s); 8.22 (1H, d, J = 8.2 Hz); 7.57 (2H, d, J = 8.5

Hz); 7.12 (1H, d, J = 8.2 Hz); 7.13 (2H, d, J = 8.5 Hz); 7.00 (2H, m); 6.98 (2H, dd, J = 9.6 Hz);
EP

13
C NMR (100 MHz, CDCl3) δ (ppm): 173.19, 146.45, 140.19, 131.76, 130.11, 127.43, 125.26,
C

124.65, 124.09, 123.52, 122.19, 120.93, 119.25, 116.53. Anal. Calc. for C16H11N2ClO: C, 67.96;
AC

H, 3.89; N, 9.91%. Found: C, 67.97; H, 3.87; N, 9.95%.

2.7.20. 4-(4-Chlorophenylazo) naphthol (3t)

C16H11N2ClO: FT-IR (KBr, cm-1) [18]: 3448 (bs), 3012, 1628, 1481, 1439, 1212, 812, 733. 1H

NMR (400 MHz, CDCl3) δ (ppm): 8.88 (1H, s,); 8.42 (1H, d, J = 8.1 Hz); 8.12 (1H, d, J = 8.6

Hz); 7.67 (2H, d, J = 8.6 Hz); 7.52 (1H, d, J = 8.1 Hz); 7.18 (2H, d, J = 8.6 Hz); 7.05 (2H, m);
12
 ACCEPTED MANUSCRIPT

6.47 (1H, d, J = 8.6 Hz); 13C NMR (100 MHz, CDCl3) δ (ppm): 172.59, 143.43, 141.11, 132.30,

132.01, 129.66, 128.84, 128.69, 128.19, 125.89, 125.33, 122.75, 118.83. Anal. Calc. for

C16H11N2ClO: C, 67.96; H, 3.89; N, 9.91%. Found: C, 67.97; H, 3.87; N, 9.95%.

PT
3. Results and discussions

3.1. Ionic liquid 6 was synthesized via the reaction of 3-chloropropyletrimethoxysilane and

RI
N,N,N',N'-tetramethylethylenediamine in acetonitrile at 80ºC in 95% yield (Scheme 2). Then the

SC
ionic liquid was immobilized on nanosilica. The immobilization was confirmed by comparison

of the FT-IR spectroscopy and EDX analysis of compounds 7 and 8 (Figure 3, A). Compound 8

U
was achieved by increasing of the length of the ionic chain via the four subsequent reactions of
AN
compound 7 with 1,4-dichlorobutane and N,N,N',N'-tetramethylethylenediamine. The structure

of compound 8 was confirmed by FT-IR spectrum, FE-SEM image, EDX and CHNSO analysis
M

(Figure 1, B and Figure 2, A). The EDX analysis showed the existence of elements C, N, Si, Cl
D

and O in the structure of 8 (Figure 3, B). Experimental N:C ratio were calculated from EDX and
TE

CHNSO analysis. Comparison of N:C ratio in two structure 7, 8 was used for approving of the

growth of the ionic chain in poly ionic compound 8. Theoretical calculation of the N:C ratio for
EP

compounds 7 and 8 showed that this ratio should be decreased by the growth of poly ionic chain.

N:C ratios (respectively from EDX and CHNSO analysis) for compounds 7 (0.259 and 0.258)
C

and 8 (0.241 and 0.246) was confirmed the growth of poly ionic chain.
AC

<<Scheme 2>>

Compound 8 was reacted with 4-chlorobuthanol in acetonitrile at 80ºC for 3 days to afford the

hydroxyl functionalized star-like poly ionic compound 9. Hydroxy to nitrite functional group

interconversion was occurred using sodium nitrite in the presence of HCl at 0-5ºC in 5 min. This

13
 ACCEPTED MANUSCRIPT

functionalizations were confirmed by comparison of the FT-IR spectra of compounds 8, 9 and 10

(Figure 2, B). The signal at 1384 cm-1 in FT-IR spectrum of product 10 was related to N=O bond

and signal O-H was weaker in the FT-IR spectrum of compound 10 in comparison with FT-IR

spectrum of the compound 9.

PT
<<Figure 1>>

RI
<<Figure 2>>

<<Figure 3>>

SC
3.2. Reactions

U
The freshly prepared compound 10 was examined as a nitrosonium source for the diazotization
AN
of aniline derivatives. Diazotization of p-nitroaniline (1mmol) in the presence of HCl 37% (2
M

mmol) at 0-5ºC was chosen as a typical reaction. Subsequent azo coupling reaction was used as

the confirmation of the formation of diazonium product. So, sodium β-naphthoxide was added to
D

the reaction mixture after diazotization for possible azo-coupling reaction and production of
TE

related azo dye, 3l. Product 3l was formed via this procedure and its structure was confirmed by
1 13
H-NMR and C-NMR spectroscopy. Using of different amount of compound 10 was used for
EP

optimization of value of this reagent and it was found that, 1.5 g of this compound was required

to achieve the highest yield of 3l from the reaction of p-nitroaniline (10 mmol) in the shortest
C

reaction time. The using of higher amounts of reagent 10 had no effect on the reaction efficiency.
AC

The generality of this promising reaction was evaluated by employing a variety of aniline

derivatives and subsequent reaction with some phenoxides. The corresponding results were

shown in Table 1. Reaction times and yields for the preparation of diazoniumes and the azo dyes

were gathered in Table 2. As seen from Table 2, the reaction proceeded smoothly to afford the

14
 ACCEPTED MANUSCRIPT

corresponding dyes in excellent yields for anilines bearing electron-withdrawing as well as

electron donating substituents. The products were purified by recrystallization with ethanol/H2O

and were identified by their spectroscopic and elemental analysis data. The reaction times and

yields were compared with those reported in the literatures (Table 2). As it can be seen from

PT
Table 2, in comparison with reported reagents, compound 10 is more effective and the reactions

RI
were accrued in higher yields and in shorter reaction times. So, this reagent acts as a catalyst in

this procedure because of its highly ionic characteristic.

SC
<<Table 1>>

U
AN
<<Table 2>>
M

In summary, a highly efficient method has been developed for the diazotization reaction of
D

anilines using nitrite functionalized poly ionic star-like compound under solvent-free conditions.

Our new introduced nitrosonium ion source is the best because it gave excellent yields in most of
TE

the cases. No by-products were formed in this new method and the purification of the desired azo
EP

dye is easier. Further work in this direction is in progress in our laboratory and will be reported

in due course of time.

C
AC

Acknowledgment

The partial financial assistance from the Research Vice Chancellor of Azarbaijan Shahid Madani

University is gratefully acknowledged.

References

15
 ACCEPTED MANUSCRIPT

[1] Hunger K. Industrial Dyes: Chemistry, Properties, Applications. 3th ed. Weinheim:

Wiley-VCH; 2003.

[2] (a) Sandborn WJ. Rational selection of oral 5-aminosalicylate formulations and

prodrugs for the treatment of ulcerative colitis. Am J Gastroenterol 2002; 97: 2939-41.

PT
(b) Sandborn WJ, Hanauer SB. Systematic review: the pharmacokinetic profiles of oral

RI
mesalazine formulations and mesalazine pro-drugs used in the management of

ulcerative colitis. Aliment Pharmacol Ther 2003; 17: 29-42. (c) Zhao R, Tan CH, Xie

SC
Y, Gao CH, Liu H, Jiang Y. One-step synthesis of azo compounds from nitroaromatics

and anilines. Tetrahedron Lett 2011; 52: 3805-9. (d) Jain A, Gupta Y, Jain SK. Azo

U
chemistry and its potential for colonic delivery. Crit Rev Ther Drug Carrier Syst 2006;
AN
23: 349-99.

[3] Roldo M, Barbu E, Brown JF, Laight DW, Smart JD, Tsibouklis J. Azo compounds in
M

colon-specific drug delivery. Expert Opin Drug Deliv 2007; 4: 547-60.

D

[4] (a) Hunger K. Industrial Dyes: Chemistry, Properties, Applications. 3th ed. Weinheim,
TE

Germany: Wiley-VCH; 2003. (b) Zollinger H. Color Chemistry: Syntheses, Properties

and Applications of Organic Dyes and Pigments. New York: VCH; 1987. (c)
EP

Gordonand PF, Gregory P. Organic Chemistry in Colour. New York: Springer; 1983.

(d) Manuela M, Raposo M, Amaro M, Belsley M. The synthesis and characterization of

C

heterocyclic azo dyes derived from 5-N,N-dialkylamino-2,2-bithiophene couplers. Dyes

AC

and Pigments 2009; 83: 59-65.

[5] Valizadeh H, Shomali A. A new nitrite ionic liquid (IL-ONO) as a nitrosonium source

for the efficient diazotization of aniline derivatives and in-situ synthesis of azo dyes.

Dyes and Pigments 2012; 92: 1138-43.

16
 ACCEPTED MANUSCRIPT

[6] Rufchahi EOM, Gilani AG. Synthesis, characterization and spectroscopic properties of

some new azo disperse dyes derived from 4-hydroxybenzo[h]quinoli-2-(1H)-one as a

new synthesized eno; type coupling component. Dyes and Pigments 2012; 95: 632-8.

[7] Baroliya PK, Mehta A, Dashora R, Chauhan RS, Goswami AK. Res. Photocatalytic

PT
cleavage of hydroxytriazenes: a solid-state synthesis of azo-dyes under sunlight

RI
irradiation. Chem Intermed 2012; 38: 2149-53.

[8] Husaain F, Hojjati M, Okamoto M, Gorga RE. Review article: Polymer-matrix

SC
Nanocomposites, Processing, Manufacturing, and Application: An Overview. Journal of

Composite Materials 2006; 40: 1511-75.

[9]
U
Li Y, Jiang Q, Wang K, Du B, Wang X. A novel and green synthesis of kojic acid
AN
derivatives in ionic liquid [bmim]BF4. Tetrahedron Lett 2013; 54: 7147-50.

[10] Rahman M, Sarkar A, Ghosh M, Majee A, Hajra A. Catalytic application of task

M

specific ionic liquid on the synthesis of benzoquinazolinone derivatives by a

D

multicomponent reaction. Tetrahedron Lett 2014; 55: 235-9.

TE

[11] Liu HW, Wilen CE. Theoretical consideration of the molecular mass distribution of star

like polymers formed by attachment of linear polymers to dendritic cores. J Polym Sci
EP

Pol Phys 2001; 39: 2751-58.

[12] Xin X, Xu G, Wang Y, Mao H, Zhang Z. Aggregation behavior of star-like PEO–PPO–

C

PEO block copolymer in aqueous solution. European Polymer Journal 2008; 44: 3246-
AC

55.

[13] Valizadeh H, Amiri M, Hosseinzadeh F. Nanoparticles of organosilane-based nitrite

ionic liquid immobilized on silica for the diazotization of aniline derivatives and

subsequent synthesis of azo dyes. Dyes and Pigments 2012; 92: 1308-13.

17
 ACCEPTED MANUSCRIPT

[14] Ajani OO, Akinremi OE, Ajani AO, Edobor-Osoh, Anake WU. Synthesis and

spectroscopic study of naphtholic and phenolic azo dyes. Physical Review & Research

International 2013; 3: 28-41.

[15] Chermahini AN, Doukheh M, Zadehhassan H, Bostanian M. Application of modified

PT
clays in diazotization and azo coupling reactions in water. J Ind Eng Chem 2012; 18:

RI
826-33.

[16] Heemstra JM, Moore JS. A novel indicator series for measuring pKa values in

SC
acetonitrile. Tetrahedron 2004; 60: 7287-92.

[17] Valizadeh H, Shomali A, Nourshargh S, Mohammad-Rezaei R. Carboxyl and nitrite

U
functionalized graphene quantum dots as a highly active reagent and catalyst for rapid
AN
diazotization reaction and synthesis of azo-dyes under solvent-free conditions. Dyes and

Pigments 2015; 113: 522-8.

M

[18] Bamoniri A, Pourali A, Nazifi M. Facile synthesis of 1-naphthol azo dyes with nano
D

SiO2/HIO4 under solvent free conditions. Bull Chem Soc Ethiop. 2013; 27: 439-45.
TE

[19] Butler RN, O’Shea PD, Shelly DP. 3-Aryl-I-tetrazol-5-yltriazenes, bench-stable

arenediazonium ion synthons: synthesis of biaryls and aryl halides. J Chem Soc Perkin
EP

Trans 1987; 1: 1039-41.

[20] Koch L, Milligan RF, Zuckerman S. Identification of some important unsulfonated azo-
C

2-naphthol dyes. Ind Eng Chem Anal Ed 1944; 16: 755-6.

AC

18
 ACCEPTED MANUSCRIPT

Table 1. Diazotization of anilines using nitrite functionalized star-like poly ionic compound and subsequent
synthesis of azo dyes.
Product
Entry Amine Coupling reagent Product
number

NH2
1 OH 3a

PT
O2N

2 Br NH2 OH 3b

RI
3 Cl NH2 OH 3c

SC
HO N
4 NH2 OH 3d
N

U
AN
Me NH2
5 OH 3e

Br
M

OH
6 O2 N NH2 3f

HO
D

OH
TE

7 Cl NH2 3g

NO2
EP

OH
8 Me NH2 3h

NO2
C

OH
AC

9 Me NH2 3i
 ACCEPTED MANUSCRIPT

Table 1. (Continued)
Product
Entry Amine Coupling reagent Product
number

OH
10 Br NH2 3j

PT
OH

RI
NH2
11 3k

O2N

SC
OH

U
12 O2 N NH2 3l
AN
OH
M

13 Cl NH2 3m
D
TE

14 NH2 NMe2 3n
EP

15 O2 N NH2 NMe2 3o
C

O2N NH2
16 NMe2 3p
AC

Cl

COOH CHO
17 3q
NH2
N
H
 ACCEPTED MANUSCRIPT

Table 1. Continued
Product
Entry Amine Coupling reagent Product
number
CHO
N
18 NH2 N
3r

N
H

PT
OH

19 3s

RI
SC
OH

20 Cl NH2 3t

U
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
Table 2. Comparison of the melting point, reaction times and yields with
reported values.

SC
Entry Product M.P (°C) Time (min) Yielda (%)
number Found Reported Diazonium Azo Found Reported
[Ref.] salts dyes [Ref.]

U
1 3a 166-167 167-169 [14] 5 5 98% 98% [14]
2 3b 216-217 216-218 [14] 5 5 87% 67% [14]
3 3c 189-191 188-190 [14] 5 5 84% 37% [14]
AN
4 3d 159-160 160-163 [4b] 5 - 88% -
5 3e 248-250 248-250 [14] 5 5 82% 42% [14]
6 3f 197-198 196-198 [5] 5 10 98% 89% [5]
7 3g 163-165 165-167 [15] 10 10 93% 80% [15]
M

8 3h 145-146 144-146 [15] 10 10 89% 78% [15]

9 3i 131-132 130-132 [19] 10 15 91% 82% [19]
10 3j 169-170 169-171 [19] 10 10 98% 81% [19]
D

11 3k 194-196 194 [20] 5 - 97% 90% [20]

12 3l 250-251 250-252 [5] 5 10 94% 89% [5]
13 3m 158-159 157-159 [19] 10 15 89% 80% [19]
TE

14 3n 107-108 108-112 [5] 5 15 84% 84% [5]

15 3o 228-230 229-230 [16] 10 15 81% 57% [16]
16 3p 192-193 191-192 [16] 10 10 86% 82% [16]
17 3q 192-194 192-195 [17] 5 10 98% 94% [17]
EP

18 3r 190-192 191-194 [17] 5 15 98% 91% [17]

19 3s 181-183 182 [18] 10 15 97% 89% [18]
20 3t 293-295 293 [18] 10 15 95% 89% [18]
a
isolated yields
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Figure 1. A) FE-SEM image of nanosilica; B) FE-SEM image of immobilized compound 8; C) FE-SEM image of
hydroxyl functionalized 9.
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Figure 2: A) FT-IR spectrum of nanosilica and poly ionic 8; B) FT-IR spectrum of poly ionic compounds 8, 9 and
10.
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Figure 3. A) EDX analysis of compound 7; B) EDX analysis of compound 8.

C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP

Scheme 1: Diazotization of anilines using NFSPI and subsequent synthesis of azo dyes.
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP

Scheme 2. Synthesis of nitrite functionalized star-like poly ionic compound.

C
AC
 ACCEPTED MANUSCRIPT

Highlights

PT
• Star-like nitrite functionalized poly ionic compound is a highly efficient

heterogeneous catalyst for the diazotization of anilines.

RI
• Azo dyes were synthesized using this catalyst in excellent yields under solvent-

SC
free conditions.

• We introduced new nitrosonium ion source and it is the best because it gave

U
excellent yields without any by-products.
AN
.
M
D
TE
C EP
AC