One pot synthesis and characterization of mono and di-substituted azo-containing amides

Article abstract of DOI:10.14233/ajchem.2015.17639

Azo-containing amides and their derivatives were synthesized by the reaction of 4-(phenyldiazenyl)aniline with different substituted benzoyl chlorides. The characterization of these synthesized compounds were based on their IR, 1H NMR spectra and elemental analysis with excellent yields.

Full text of DOI:10.14233/ajchem.2015.17639

Asian Journal of Chemistry; Vol. 27, No. 6 (2015), 2001-2004
A
SIAN
J
OURNAL OF HEMISTRY
C
http://dx.doi.org/10.14233/ajchem.2015.17639
One Pot Synthesis and Characterization of Mono and Di-Substituted Azo-Containing Amides
1,*
2,*
1
1
3,4
RASHEED AHMAD KHERA , MUNAWAR IQBAL , M. ASIF TAHIR , M. ASIF HANIF and PETER LANGER
1Department of Chemistry, University of Agriculture, Faisalabad-38040, Pakistan
2National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar-25120, Pakistan
3Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany
4Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
*Corresponding authors: E-mail: rasheedahmadkhera@yahoo.com; bosalvee@yahoo.com
Received: 21 March 2014;
Accepted: 31 May 2014;
Published online: 17 March 2015;
AJC-16946
Azo-containing amides and their derivatives were synthesized by the reaction of 4-(phenyldiazenyl)aniline with different substituted
benzoyl chlorides. The characterization of these synthesized compounds were based on their IR, 1HNMR spectra and elemental analysis
with excellent yields.
Keywords: 4-(Phenyldiazenyl)aniline, Amidation, N-protection, N-acylation.
cations of azo group containing compounds are optical data
storage. Generally, phthalocyanine dyes, cyanine dyes and
metaleazo complex dyes are used for DVD-R (digital versatile
disc-recordable) as well as footage layer20-22. Phthalocyanine
dyes also have disadvantages, such as poorly soluble and
elevated expenditure than cyanine dyes23-25. In contrast, metal-
azo composite and organic azo compounds are extra stable
than cyanine dyes against light, offer uncomplicated control
of the wavelength according to the different substituted groups
and boast tremendous thermal reliability with a metal comp-
lex26,27. Based upon these reflections of beyond requirements,
the synthesis of azo compounds engaged an important role in
fabric chemistry28-30. Due to the significant importance of azo-
containing compounds and prolongation of our interest in
syntheses of azo-based compounds, we report herein the
synthesis of new azo containing amides.
INTRODUCTION
Amides, ureas and sulfonamides are used everywhere for
structural enhancement within drug design and discovery. The
catalytically C-C and C-N bonds formation is a vigorous theme
in the field of current organic synthesis1-3. Amides are among
the great consequence functional groups in natural products,
polymers and pharmaceuticals lead compounds4,5. Their value
in organic, biological and fabric chemistry directive the deve-
lopment of more economical methods for their synthesis of
these compounds5,6. In general, aliphatic, aromatic and hetero-
aromatic amides can be synthesized from the reaction between
carboxylic acids or their derivatives with amines7. Rovis and
Bode and their co-workers reported amidation with N-hetero-
cyclic carbenes (NHCs) as catalyst8. Azo containing comp-
ounds, with two phenyl rings alienated by an azo (-N=N-)
bond, are multipurpose molecules and highly acknowledged
in research vicinity both fundamental and relevance. The strong
electronic absorption utmost can be adapted by different ring
substitution to fall ultraviolet to red-visible regions, allocating
chemically fine-tuning of dyes9-12. This collective fact that azo
groups are comparatively vigorous and chemically stable has
provoked extensive study of azobenzene support structures as
dyes as well as colorant13-17. In addition, the light stimulated
interconversion permit the system integrating azo group to be
used as photo switches, consequence rapid and reversible
control over a diversity of chemical, electronic, mechanical and
optical properties18,19. Because of the high quality of thermal
constancy of azo compounds, one of the most essential appli-
EXPERIMENTAL
General procedure for synthesis of 4a-g and 5a-g: The
reaction was carried out in a two neck flask. 4-(Phenyldiazenyl)-
aniline in Et3N with different substituted aromatic benzoyl
chlorides and aliphatic carbonyl chlorides at room temperature.
On cooling the reaction mixture was diluted with chloroform
and washed with 10 % HCl solution31,32. The organic layer dried
over anhydrous Na2SO4 and concentrated under reduces pressure.
The resulting residue was purified by column chromatography
(silica gel, EtOAc/heptanes).
N-[4-(Phenyldiazenyl)phenyl]benzamide (4a): Starting
with 4-(phenyldiazenyl)aniline (2) (197 mg, 1 mmol), benzoyl

2002 Khera et al.
Asian J. Chem.
chloride (154 mg, 1.1 mmol), according to the general proce-
to the general procedure A, 4f was isolated as a redish solid
(271 mg, 83 %). Reaction at room temperature for 10 min.
m.p. = 177-178 °C. 1H NMR (250 MHz, CDCl3): δ = 6.93(d,
J = 17.5 Hz, 1H), 7.19-7.21 (m, 2H, ArH), 7.43 (d, J = 17.4
Hz, 1H), 7.37-7.39 (m, 2H, ArH), 7.57-7.61 (m, 4H, ArH),
7.96-7.98 (m, 2H, ArH), 7.79 (d, J = 7.8 Hz, 2H, ArH), 8.34
dure A, 4a was isolated as a redish solid (253 mg, 84 %).
1
room temperature for 10 min. m.p. = 158-159 °C. H NMR
(250 MHz, CDCl3): δ = 7.17-7.19 (m, 1H, ArH), 7.60-7.69
(m, 5H, ArH), 7.74-7.78 (m, 4H, ArH), 8.04 (d, J = 7.8 Hz,
2H), 8.17 (d, J = 7.5 Hz, 2H,ArH), 9.8 (bs, 1H). IR (KBr, νmax
,
cm-1): 3324 (NH), 1643 (CO). Anal. Calcd. for C19H15N3O: C
75.73, H 5.02, N 13.94; found: C 75.61, H 4.99, N 13.86.
2-Methyl-N-(4-(phenyldiazenyl)phenyl)benzamide
(4b): Starting with 4-(phenyldiazenyl)aniline (2) (197 mg,
1 mmol), 2-methylbenzoyl chloride (169 mg, 1.1 mmol),
according to the general procedure A, 4b was isolated as a
redish solid (249 mg, 79 %). Reaction at room temperature
for 10 min. m.p. = 197-198 °C. 1H NMR (250 MHz, CDCl3):
δ = 2.51 (s, 3H), 7.16-7.18 (m, 2H, ArH), 7.22-7.24 (m, 1H),
7.58-7.66 (m, 6H, ArH), 7.73 (d, J = 7.4 Hz, 2H), 8.15 (d, J =
7.6 Hz, 2H,ArH), 10.15 (bs, 1H). Elemental analysis: C, 76.17;
H, 5.43; N, 13.32. IR (KBr, νmax, cm-1): 3322 (NH), 1641 (CO).
Anal. Calcd. for C20H17N3O: C 76.17, H 5.43, N 13.32; found:
C 76.06, H 5.42, N 13.21.
(d, J = 7.7 Hz, 2H, ArH), 10.01 (bs, 1H, NH). IR (KBr, νmax,
cm-1): 3316 (NH), 1641 (CO). Anal. Calcd. for C21H17N3O: C
77.04, H 5.23, N 12.84; found: C 77.01, H 5.19, N 12.71.
N-(4-(Phenyldiazenyl)phenyl)octanamide (4g): Starting
with 4-(phenyldiazenyl)aniline (2) (197 mg, 1 mmol), octanoyl
chloride (178 mg, 1.1 mmol), according to the general proce-
dure A, 4g was isolated as a redish solid (252 mg, 78 %).
Reaction at room temperature for 10 min. m.p. = 89-90 °C. 1H
NMR (250 MHz, CDCl3): δ = 0.78 (t, J = 7.7Hz, 3H,
CH3CH2(CH2)6), 1.27-1.34 (m, 8H, CH3(CH2)4(CH2)3), 1.56-
1.58 (m, 2H, CH3CH2(CH2)6), 2.37 (t, J = 7.4 Hz, 2H,
CH3CH2(CH2)6), 7.14-7.16 (m, 1H, ArH), 7.61-7.63 (m, 2H,
ArH), 7.72 (d, J = 7.6 Hz, 2H, ArH), 7.97-7.99 (m, 2H, ArH),
8.25 (d, J = 7.8 Hz, ArH), 10.03 (bs, 1H). IR (KBr, νmax, cm-1):
3324 (NH), 1643 (CO). Anal. Calcd. for C20H25N3O: C 74.27,
H 7.79, N 12.99; found: C 74.21, H 7.73, N 12.92.
3-Methyl-N-(4-(phenyldiazenyl)phenyl)benzamide
(4c): Starting with 4-(phenyldiazenyl)aniline (2) (197 mg,
1 mmol), 3-methylbenzoyl chloride (169 mg, 1.1 mmol),
according to the general procedure A, 4c was isolated as a
redish solid (255 mg, 81 %). Reaction at room temperature
for 10 min. m.p. = 193-194 °C. 1H NMR (250 MHz, CDCl3):
δ = 2.36 (s, 3H), 7.21-7.23 (m, 2H, ArH), 7.34-7.36 (m, 1H,
ArH), 7.43 (d, J = 7.7 Hz, 1H, ArH), 7.61-7.64 (m, 2H), 7.73
(d, J = 7.6 Hz, 2H), 7.78-7.81 (m, 2H, ArH), 7.84 (d, J = 7.6
Hz, 2H, ArH), 8.23 (d, J = 7.7 Hz, 2H, ArH), 10.14 (bs, 1H).
IR (KBr, νmax, cm-1): 3325 (NH), 1645 (CO). Anal. Calcd. for
C20H17N3O: C 76.17, H 5.43, N 13.32; found: C 76.14, H 5.41,
N 13.30.
4-Methyl-N-(4-(phenyldiazenyl)phenyl)benzamide
(4d): Starting with 4-(phenyldiazenyl)aniline (2) (197 mg,
1 mmol), 4-methylbenzoyl chloride (169 mg, 1.1 mmol),
according to the general procedure A, 4d was isolated as a
redish solid (252 mg, 80 %). Reaction at room temperature
for 10 min. m.p. = 197-198 °C. 1H NMR (250 MHz, CDCl3):
δ = 2.31 (s, 3H, CH3), 7.18-7.19 (m, 1H, ArH), 7.39-7.41 (m,
2H), 7.63-7.65 (m, 2H, ArH), 7.69 (d, J = 7.6 Hz, 2H), 8.13
(d, J = 7.8Hz, 2H, ArH), 10.14 (bs, 1H). IR (KBr, νmax, cm-1):
3319 (NH), 1640 (CO). Anal. Calcd. for C20H17N3O: C 76.17,
H 5.43, N 13.32; found: C 76.13, H 5.41, N 13.30.
N-Benzoyl-N-(4-(phenyldiazenyl)phenyl)benzamide
(5a): Starting with 4-(phenyldiazenyl)aniline (2) (197 mg,
1 mmol), benzoyl chloride (308 mg, 2.2 mmol), according to
the general procedureA, 5a was isolated as a redish solid (336
mg, 83 %). Reaction temperature 45 °C for 4 h. m.p. = 136 °C.
1H NMR (250 MHz, CDCl3): δ = 7.23-7.24 (m, 1H, ArH),
7.60-7.98 (m, 14H, ArH), 8.03 (m, 2H, ArH), 8.26 (m, 2H,
ArH). IR (KBr, νmax, cm-1): 1641 (CO). Anal. Calcd. for
C26H19N3O2: C 77.02, H 4.72, N 10.36; found: C 77.00, H 4.69,
N 10.31.
2-Methyl-N-(2-methylbenzoyl)-N-(4-(phenyldiazenyl)-
phenyl)benzamide (5b): Starting with 4-(phenyldiazenyl)-
aniline (2) (197 mg, 1 mmol), 2-methylbenzoyl chloride (339
mg, 2.2 mmol), according to the general procedure A, 5b was
isolated as a redish solid (329 mg, 76 %). Reaction temperature
45 °C for 4 h. m.p. = 148 °C. 1H NMR (250 MHz, CDCl3): δ
= 2.46 (s, 6H, 2 × CH3), 7.13-7.16 (m, 4H, ArH), 7.23-7.24
(m, 1H,ArH), 7.55-7.57 (m, 2H,ArH), 7.63-7.65 (m, 2H,ArH),
7.71-7.72 (m, 2H, ArH), 7.89-7.90 (m, 2H, ArH), 7.97-7.98
(m, 2H, ArH), 8.27-8.29 (m, 2H, ArH). IR (KBr, νmax, cm-1):
1637 (CO) cm-1. Anal. Calcd. for C28H23N3O2 : C 77.58, H
5.35, N 9.69; found: C 77.43, H 5.29, N 9.54.
2-Chloro-N-(4-(phenyldiazenyl)phenyl)benzamide
(4e): Starting with 4-(phenyldiazenyl)aniline (2) (197 mg,
1 mmol), 2-chlorobenzoyl chloride (192 mg, 1.1 mmol), accor-
ding to the general procedure A, 4e was isolated as a redish
solid (298 mg, 89 %). Reaction at room temperature for 10
3-Methyl-N-(3-methylbenzoyl)-N-(4-(phenyldiazenyl)-
phenyl)benzamide (5c): Starting with 4-(phenyldiazenyl)-
aniline (2) (197 mg, 1 mmol), 3-methylbenzoyl chloride (339
mg, 2.2 mmol), according to the general procedure A, 5c was
isolated as a redish solid (342 mg, 79 %). Reaction temperature
45 °C for 4 h. m.p. = 154 °C. 1H NMR (250 MHz, CDCl3): δ
= 2.36 (s, 3H), 7.23-7.24 (m, 1H, ArH), 7.39-7.41 (m, 2H,
ArH), 7.49-7.52 (m, 3H, ArH), 7.63-7.65 (m, 2H), 7.74 (m,
3H, ArH), 7.83-7.85 (m, 2H, ArH), 7.98-8.00 (m, 2H, ArH),
8.27-8.29 (m, 2H,ArH). IR (KBr, νmax, cm-1): 1640 (CO).Anal.
Calcd. for C28H23N3O2 : C 77.58, H 5.35, N 9.69; found: C
77.49, H 5.31, N 9.61.
1
min. m.p. = 213-214 °C. H NMR (250 MHz, CDCl3): δ =
7.20-7.22 (m, 1H, ArH), 7.44-7.45 (m, 1H), 7.53-7.54 (m, 1H,
ArH), 7.66-7.70 (m, 4H, ArH), 7.78-7.80 (m, 2H, ArH), 8.01-
8.04 (m, 2H, ArH), 8.33-8.35 (m, 2H, ArH), 10.23 (bs, 1H).
IR (KBr, νmax, cm-1): 3327 (NH), 1648 (CO). Anal. Calcd. for
C19H14N3OCl: C 67.96, H 4.20, N 12.51; found: C 67.92, H
4.17, N 12.43.
3-Phenyl-N-(4-((E)-phenyldiazenyl)phenyl)acrylamide
(4f): Starting with 4-(phenyldiazenyl)aniline (2) (197 mg,
1 mmol), cinnamyl chloride (183 mg, 1.1 mmol), according
4-Methyl-N-(4-methylbenzoyl)-N-(4-(phenyldiazenyl)-
phenyl)benzamide (5d): Starting with 4-(phenyldiazenyl)-
aniline (2) (197 mg, 1 mmol), 4-methylbenzoyl chloride (339

Vol. 27, No. 6 (2015)
One Pot Synthesis and Characterization of Mono and Di-Substituted Azo-Containing Amides 2003
mg, 2.2 mmol), according to the general procedure A, 5d was
isolated as a redish solid (355 mg, 82 %). Reaction temperature
45 °C for 4 h. m.p. = 157 °C. 1H NMR (250 MHz, CDCl3): δ
= 2.33 (s, 6H, 2 × CH3), 7.21-7.23 (m, 1H, ArH), 7.37-7.40
(m, 4H,ArH), 7.62-7.64 (m, 2H,ArH), 7.71-7.73 (m, 2H,ArH),
7.86-7.89 (m, 4H, ArH), 8.02-8.04 (m, 2H, ArH), 8.30-8.32
(m, 2H, ArH). IR (KBr, νmax, cm-1): 1638 (CO). Anal. Calcd.
for C28H23N3O2: C 77.58, H 5.35, N 9.69; found: C 77.49, H
5.28, N 9.54.
2-Chloro-N-(2-chlorobenzoyl)-N-(4-(phenyldiazenyl)-
phenyl)benzamide (5e): Starting with 4-(phenyldiazenyl)-
aniline (2) (197 mg, 1 mmol), 2-chlorobenzoyl chloride (380
mg, 2.2 mmol), according to the General procedure A, 5e was
isolated as a redish solid (431 mg, 91 %). Reaction temperature
45 °C for 4 h. m.p. = 183 °C. 1H NMR (250 MHz, CDCl3): δ
= 7.25-7.26 (m, 1H, ArH), 7.41-7.43 (m, 2H, ArH), 7.49-7.51
(m, 2H,ArH), 7.63-7.66 (m, 4H,ArH), 7.71-7.73 (m, 2H,ArH),
7.75-7.77 (m, 2H, ArH), 8.01-8.03 (m, 2H, ArH), 8.31-8.33
(m, 1H, ArH). IR (KBr, νmax, cm-1): 1653 (CO). Anal. Calcd.
for C26H17Cl2N3O2: C 65.83, H 3.61, N 8.86; found: C 65.78,
H 3.54, N 8.79.
Different mono substituted N-(4-(phenyldiazenyl)phenyl)-
benzamide (4a-g) were prepared in 79-89 % yields by the
reaction of 4-(phenyldiazenyl)aniline (2) with 1.1 equiv. of diffe-
rent substituted benzoyl chlorides 3a-g (Scheme-II, Table-1).
The best yields were obtained when the reactions were carried
out using NEt3 and DIPA as the base as well as solvent, while
employment of other base, such as NaOH, KOH resulted in a
decrease of the yield. The use of potassium phosphate (K3PO4)
as the base and 1,4-dioxane as a solvent gave optimal yields.
The best yield was obtained for the reaction of simple benzoyl
chlorides. The lowest yield was obtained for 4-methyl chlorides
which might be attributed to its high nucleophilicity (due to
the electron-donating methyl group).
H
N
R
NH2
+
O
N
O
N
N
Cl
N
R
3(a-g)
2
4(a-g)
Scheme-II: Synthesis of 4a-g. Reagents and conditions: i) 2 (1 equiv.), 3a-g
(1.1 equiv.) at room temperature for 10 min (R is representing
aryl and alkyl groups)
N-Cinnamoyl-N-(4-((E)-phenyldiazenyl)phenyl)-
cinnamamide (5f): Starting with 4-(phenyldiazenyl)aniline
(2) (197 mg, 1 mmol), cinnamoylbenzoyl chloride (334 mg,
2.2 mmol), according to the general procedure A, 5f was
isolated as a redish solid (370 mg, 81 %). Reaction temperature
45 °C for 4 h. m.p. = 169 °C. 1H NMR (250 MHz, CDCl3): δ
= 6.72 (d, J = 17.5 Hz, 2H), 7.21-7.23 (m, 1H, ArH), 7.34-
7.37 (m, 4H, CHAr), 7.41 (d, J = 17.6 Hz, 1H), 7.57-7.59 (m,
4H, ArH), 7.63-7.65 (m, 2H, ArH), 7.75-7.77 (m, 2H, CHAr),
8.01-8.03 (m, 2H, CHAr), 8.29-8.31 (m, 2H, CHAr). IR (KBr,
TABLE-1
SYNTHESIS OF MONO-ARYL AND
ALKYL DIAZO-BENZAMIDE (4a-g)
R
4
a
% (4)a
84
C6H5
2-MeC6H4
3-MeC6H4
4-MeC6H4
2-ClC6H4
C8H7
79
81
80
89
b
c
d
e
ν
max, cm-1): 1640 (CO). Anal. Calcd. for C30H23N3O2: C 78.75,
H 5.07, N 9.18; found: C 78.70, H 4.98, N 9.05.
83
f
C7H15
78
g
aYield of isolated products
(E)-N-Octanoyl-N-(4-(phenyldiazenyl)phenyl)octan-
amide (5g): Starting with 4-(phenyldiazenyl)aniline (2) (197
mg, 1 mmol), octanoyl-chloride (356 mg, 2.2 mmol), according
to the general procedure A, 5g was isolated as a redish solid
(332 mg, 74 %). Reaction temperature 45 °C for 4 h. m.p. =
175 °C. 1H NMR (250 MHz, CDCl3): δ = 0.78 (t, J = 7.7 Hz,
4H, CH3CH2(CH2)6), 1.23-1.30 (m, 16H, CH3(CH2)4(CH2)3),
1.53-1.55 (m, 4H, CH3CH2(CH2)6), 2.35 (t, J = 7.4 Hz, 4H,
CH3CH2(CH2)6), 7.13-7.15 (m, 2H, ArH), 7.59-7.62 (m, 4H,
ArH), 7.71 (d, J = 7.4 Hz, 2H, ArH), 7.95-7.97 (m, 2H, ArH),
8.23 (d, J = 7.7 Hz, ArH). IR (KBr, νmax, cm-1): 1638 (CO).
Anal. calc. for C28H39N3O2: C 74.80, H 8.74, N 9.35; found: C
74.73, H 8.68, N 9.23.
The amidation of 4-(phenyldiazenyl)aniline (2) with an
equimolar ratio of different substituted benzoyl chlorides 3a-g
(2.2 equiv.) afforded the disubstituted N-benzoyl-N-(4-(phenyl-
diazenyl)phenyl)benzamide 5a-g in 76-91 % yield (Table-2,
Scheme-III). The yields of the products derived from chloro
derivative 5e were generally higher than those of others
derivatives which might be explained by the high stability of
the chloro group. No clear trend was observed for the depen-
dence of the yields from the type of benzoyl chloride employed.
The one-pot reaction of 5a-g were also carried out by the
addition of different substituted aryl or alkyl benzoyl chlorides,
which were afforded two fold di-substituted arylated/alylated
aiazobenzamides 5a-g, at 90 °C for 4 h to achieve good yield.
These reactions were successful for both electron-rich and
RESULTS AND DISCUSSION
4-(Phenyldiazenyl)aniline (2) was prepared in 80 % yield
by the reaction of commercially available aniline (1) with
NaNO2 under acedic media (Scheme-I).
O
R
O
N
R
NH2
NH2
+
O
N
NH2
N
NaNO2/HCl
0-5 °C
N
N
N
Cl
N
R
2
3(a-g)
5(a-g)
2
1
Scheme-III: Synthesis of 5a-g; Reagents and conditions: i, 2 (1.0 equiv.),
3a-g (2.2 equiv.), 4 h (R is representing aryl and alkyl groups)
Scheme-I:Synthesis of 4-(phenyldiazenyl)aniline (2). Reagents and conditions:
i, Aniline (1) (2.0 equiv), -0-5 °C, distilled water NaNO2/HCl

2004 Khera et al.
Asian J. Chem.
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TABLE-2
SYNTHESIS OF BIS-ARYL AND
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ALKYL DIAZOBENZAMIDE (5a-g)
4
a
b
c
d
e
f
% (5)a
83
76
79
82
91
81
74
R
C6H5
2-MeC6H4
3-MeC6H4
4-MeC6H4
2-ClC6H4
C8H7
C7H15
g
aYield of isolated products
electron-poor benzoyl chlorides as shown in Scheme-III and
Table-2. During the optimization, it proved to be important
that the first step was carried out at 45 °C for 10 min to achieve
a good selectivity 4a-g. All reactions proceeded in excellent
yield.
Conclusion
In conclusion, we reported an efficient method for the
synthesis different azo amidation of 4-(phenyldiazenyl)aniline
with different substituted aromatic benzoyl chlorides and
aliphatic carbonyl chlorides to get different mono- and N-
protected di- azo-containg amides which provide a convenient
and sequential azo-amidation.
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ACKNOWLEDGEMENTS
The authors are gratefully acknowledged to the Higher
Education Commission (HEC), Pakistan.
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