Synthesis of some new substituted oxiranes from 4′-hydroxy-3′, 5′-dinitrochalcones and their sulfanilic acid-catalyzed aminolysis

Article abstract of DOI:10.1007/s11164-012-0982-2

A new series of (4′-hydroxy-3′,5′-dinitrophenyl) (3-aryloxiran-2-yl) methanone derivatives has been synthesized by the reaction of 4′-hydroxy-3′,5′-dinitro-substituted chalcones and alkaline H₂O₂. The resulted oxiranes on sulfanilic acid-catalyzed aminolysis afforded 2-hydroxy-1-(4′-hydroxy-3′,5′- dinitrophenyl)-3-aryl-3-(arylamino) propan-1-one derivatives. The advantage of this environmentally benign safe protocol offers a simple reaction set-up, mild reaction conditions, high product yields and short reaction time. The catalyst was reused several times without significant loss of catalytic activity.

Full text of DOI:10.1007/s11164-012-0982-2

Res Chem Intermed
DOI 10.1007/s11164-012-0982-2
Synthesis of some new substituted oxiranes
from 40-hydroxy-30,50-dinitrochalcones
and their sulfanilic acid-catalyzed aminolysis
•
Biresh Kumar Nitu S. Rathore K. L. Ameta
•
Received: 14 November 2012 / Accepted: 15 December 2012
Ó Springer Science+Business Media Dordrecht 2013
Abstract A new series of (40-hydroxy-30,50-dinitrophenyl) (3-aryloxiran-2-yl)
methanone derivatives has been synthesized by the reaction of 40-hydroxy-30,50-
dinitro-substituted chalcones and alkaline H2O2. The resulted oxiranes on sulfanilic
acid-catalyzed aminolysis afforded 2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-
aryl-3-(arylamino) propan-1-one derivatives. The advantage of this environmentally
benign safe protocol offers a simple reaction set-up, mild reaction conditions, high
product yields and short reaction time. The catalyst was reused several times
without significant loss of catalytic activity.
Keywords Chalcone ꢀ Alkaline H2O2 ꢀ Epoxide ꢀ Ring opening ꢀ Sulfanilic acid
Introduction
Owing to the chemistry of chalcones containing a,b-unsaturated carbonyl, their
functionality makes them biologically active precursors for the synthesis of different
sized bioactive heterocycles of physiological importance [1–3]. Oxiranes are the
most versatile intermediates in various organic syntheses, as they can be easily
prepared from a variety of other functional groups [4]. Due to their ring strain and
high reactivity, their reactions with various nucleophiles lead to highly regio- and
stereoselective ring openings [5–7]. Aminolysis of the epoxide ring has attracted
significant attention from organic chemists in the past few years. It mainly involves
monohaptic nucleophiles and the use of different catalysts such as metal halides [8],
polymer supported [9], montmorillonite K10 [10], metal salt [11], and different
B. Kumar ꢀ N. S. Rathore ꢀ K. L. Ameta (&)
Department of Chemistry, FASC, Mody Institute of Technology & Science, Lakshmangarh 332311,
Rajasthan, India
e-mail: klameta77@hotmail.com
123

B. Kumar et al.
reaction media such as fluoro alcohols [12], ionic liquids [13], water [14] and
solvent-free conditions [15].
Recently, heterogeneous catalysts have attracted increasing interest due to
economic and environmental considerations. Sulfanilic acid is one such and has
been explored as a powerful catalyst for various organic transformations under mild
conditions [16, 17]. Chalcones 1 on treatment with alkaline H2O2 in methanol
yielded intermediate (40-hydroxy-30,50-dinitrophenyl) (3-aryloxiran-2-yl)methanone
derivatives 2, which on sulfanilic acid-catalyzed aminolysis afforded 2-hydroxy-1-
(40-hydroxy-30,50-dinitrophenyl)-3-aryl-3-(arylamino) propan-1-ones 3 as the sole
product in good yield.
Results and discussion
The present study describes sulfanilic acid-catalyzed aminolysis of (40-hydroxy-
30,50-dinitrophenyl) (3-aryloxiran-2-yl) methanone derivatives 2 (Scheme 1). The
starting compounds 1a–j (40-hydroxy-30,50-dinitrochalcones) were synthesized by
the condensation of 4-hydroxy-3,5-dinitroacetophenone with variously substituted
aromatic aldehydes using conventional [3] and microwave irradiated method [18].
Chalcones 1a–j on treatment with H2O2 (30 %), NaOH (4 M) in methanol via
stirring workup at optimum temperature gave (40-hydroxy-30,50-dinitrophenyl) (3-
aryloxiran-2-yl) methanone derivatives 2a–j. The mechanism involves the reaction
of HOO2 (generated by the reaction of H2O2 ? NaOH) which may attack the b-
carbon of the conjugated system to give intermediates, followed by the conversion
to trans-epoxides [19]. The structures of the cyclized products (2a–j) have been
elucidated by microanalysis FTIR and 1H NMR (Fig. 1). The FTIR spectra showed
the presence of a strong absorption band at 1,670–1,690 cm-1 which is attributed to
the carbonyl group. A medium absorption band appeared at 1,065–1,080 cm-1
confirming the presence of an epoxide ring, and 1H NMR spectra shows
characteristic peaks at 4.40–4.50 (d, aH, J = 1.6 Hz) and 4.10–4.21 (d, bH,
J = 1.6 Hz).
The intermediate (40-hydroxy-30,50-dinitrophenyl) (3-aryloxiran-2-yl) methanon-
es 2a–j treated with substituted anilines in dioxane at 90 °C in the presence of
sulfanilic acid afforded corresponding 3a–o in good yields. Recently, intensive
studies have been focused on the development of catalytic systems, owing to their
importance in synthetic organic chemistry. One of the most attractive synthetic
strategies favored by organic chemists is the use of heterogeneous catalysts in
increasing the efficiency of a wide range of organic syntheses [20].
Sulfanilic acid is a dry, non-volatile, non-hydroscopic, odorless and white stable
crystalline solid. During aminolysis, aromatic amines with electron-donating
substituents react quite fast as compared to aromatic amines with electron-
withdrawing substituents, as well as sterically hindered aniline. The sulfanilic acid-
catalyzed conditions were then extended to a variety of 1,2-epoxides.
The reaction was optimized for various parameters such as temperature, solvent, and
catalyst loading. The effect of temperature on the yield of products was monitored from
room temperature to 100 °C. However, no further increase in the yield was obtained by
123

Synthesis of some new substituted oxiranes
Ar
Ar'
HN
Ar
Ar
O
O
O
O
H2O2 (30%), NaOH (4M)
Ar'-NH2
OH
Methanol
Sulphanilic acid 10 (mol%)
Stirring workup
Dioxane, 90oC
NO2
O2N
NO2
O2N
Stirring workup
O2N
NO2
OH
OH
OH
(3a-o)
(2a-j)
(1a-j)
Ar
Ar
Ar'
3a = C6H5
3-CH3-C6H4
2a = C6H5
3b = 2-Cl-C6H4
3c = 3-Cl-C6H4
3d = 4-Cl-C6H4
3e = 4-OCH3-C6H4
3-CH3-C6H4
3-CH3-C6H4
3-CH3-C6H4
3-CH3-C6H4
2b = 2-Cl-C6H4
2c = 3-Cl-C6H4
2d = 4-Cl-C6H4
2e = 4-OCH3-C6H4
3f = 3,4-(OCH3)2-C6H3
3-CH3-C6H4
2f = 3,4-(OCH3)2-C6H3
2g = 3,4,5-(OCH3)3-C6H2
2h = 4-CH3-C6H4
3g = 3,4,5-(OCH3)3-C6H2 3-CH3-C6H4
3h = 4-CH3-C6H4
3i = 2-Br-C6H4
3j = 4-Br-C6H4
3k = C6H5
3-CH3-C6H4
3-CH3-C6H4
3-CH3-C6H4
C6H5
2i = 2-Br-C6H4
2j = 4-Br-C6H4
3l = C6H5
3-NO2-C6H4
3m = 3,4-(OCH3)2-C6H3 3-NO2-C6H4
3n = 3,4-(OCH3)2-C6H3
3o = 2-Br-C6H4
3-Br-C6H4
3-NO2-C6H4
Scheme 1 Synthesis of the title compounds
Fig. 1 Explanation of FTIR and
1H NMR spectral data of
intermediate (40-hydroxy-30,50-
dinitrophenyl) (3-aryloxiran-2-
yl) methanone derivatives
O
H
O
H
O N
2
Ar
HO
NO
2
increasing the temperature from 90 to 100 °C. Hence, 90 °C was chosen as the optimum
reaction temperature. An attempt to catalyze the reaction in the absence of solvent resulted
in nil yield. Among the various solvents studied, dioxane was found to be the best solvent
(Table 1) giving maximum yield of desired products. Catalyst concentration was also
optimized by varying it from 3 to 15 mol%. An increase in the product yield was observed
for 3–10 mol% of catalyst amount. Hence, 10 mol% was considered as an optimum
catalyst concentration (Table 2). To our delight, under the above optimized conditions,
the reaction proceeds smoothly and a variety of the desired 2-hydroxy-1-(40-hydroxy-
30,50-dinitrophenyl)-3-aryl-3-(arylamino) propan-1-one derivatives were obtained in
excellent yields (Table 3). The FTIR spectrum confirms this transformation by showing
the sharp peak of [C=O at 1,670–1,690 cm-1, NH at 3,310–3,340 cm-1, and a broad
peak of –OH at 3,400–3,450 cm-1. The1H NMR also justifies the same by showing peaks
at 6.25–6.40 (br, s, 1H, –CH–OH), 5.45–5.60 (d, aH, J = 2.15 Hz), 4.60–4.75 (d, bH,
J = 2.15 Hz), and 3.15–3.35 (s, 1H, –NH–) (Fig. 2).
123

B. Kumar et al.
Table 1 Effect of solvent for the synthesis of 2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-aryl-3-
(arylamino) propan-1-onesa
Entry
Solvents
Yield (%)
1
2
3
4
5
a
None
Nil
20
75
30
92
CH3Cl
CH3CN
CH2Cl2
Dioxane
Reaction conditions: (40-hydroxy-30,50-dinitrophenyl) (3-aryloxiran-2-yl)methanone (0.02 mol), aro-
matic amine (0.02 mol) and sulfanilic acid (10 mol%) in dioxane (15 ml) at 90 °C temperature for 2 h
Table 2 Effect of catalyst loading for the synthesis of 2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-
aryl-3-(arrylamino)propan-1-onesa
Entry
Catalyst (mol%)
Yield (%)
1
2
3
4
a
3
5
45
60
92
92
10
15
Reaction conditions: (40-hydroxy-30,50-dinitrophenyl) (3-aryloxiran-2-yl) methanone (0.02 mol), aro-
matic amine (0.02 mol) and sulfanilic acid (10 mol%) in dioxane (15 ml) at 90 °C temperature for 2 h
The reusability of the catalysts is one of the most important benefits and makes
them useful for commercial applications. Thus, the recovery and reusability of the
catalyst was investigated. The recyclability of the catalyst during the aminolysis of
1,2-epoxides in the presence of sulfanilic acid (10 mol%) was checked (Table 4).
The separated catalyst can be reused after washing with ethanol and drying at
100 °C for 2 h. The catalyst was used in the mentioned reaction five times; some
activity such as fresh catalyst was reduced in the fifth run (Table 4).
Materials and methods
All chemicals were purchased from Sigma-Aldrich and Merck (AR grade) and were
1
used without further purification. H and 13C NMR spectra were recorded using
(CDCl3) at 400 and 100 MHz, respectively, on a FT-NMR spectrometer Bruker AV
III. The chemical shifts are denoted in d units (ppm) relative to TMS (d = 0.00) for
protons 1H: s (singlet), br (broad singlet), d (doublet), and m (multiplet). Melting
points (°C) were measured in open glass capillaries using a Veego (VMP-MP)
melting point apparatus and are uncorrected. Infrared spectra (m, cm-1) were
recorded on a Perkin-Elmer spectrophotometer model RX I. Elemental analyses (C,
H, N) were in full agreement with the proposed structures within 0.4 % of the
theoretical values on a Carlo Erba 1108 analyzer. Monitoring of the reaction and
checking the purity of the final products were carried out by thin layer
123

Synthesis of some new substituted oxiranes
Table 3 Yields of 2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-aryl-3-(arylamino) propan-1-ones
with reaction time
Ar'
HN
Ar
O
OH
O2N
NO2
OH
(3a-o)
Entry
Time (h)
Yield (%)
Entry
Time (h)
Yield (%)
3a
3b
3c
3d
3e
3f
2
88
90
88
92
90
86
87
82
3i
3j
2
84
85
80
72
60
88
65
2
2
1.5
1.5
1
3k
3l
2.5
4
3m
3n
3o
4
1
2
3g
3h
1
3.5
1.5
Fig. 2 Explanation of FTIR and
1H NMR spectral data of
2-hydroxy-1-(40-hydroxy-30,50-
dinitrophenyl)-3-aryl-3-
(arylamino) propan-1-one
derivatives
Ar'
HN
O
H
O2N
HO
Ar
H
HO
NO 2
chromatography (TLC) using silica gel precoated aluminium sheets (Merck; 60–120
mesh) and visualization with ultraviolet light at 365 and 254 nm.
General procedure for the synthesis of intermediate
(40-hydroxy-30,50-dinitrophenyl) (3-aryloxiran-2-yl) methanones (2a–j)
An amount of 2.0 mmol of the chalcones was dissolved in 2.0 ml of methanol in a
round-bottom flask equipped with a magnetic stirring bar. Next, 0.60 ml of 30 %
H2O2 was added with stirring and the flask cooled to 15–20 °C in an ice-water bath.
Then, 0.25 ml of 4 M NaOH was added drop-wise with stirring over a period of
5–10 min. After the completion of the reaction (progress of the reaction was
monitored by TLC, eluent: n-hexane–EtOAc 8:2 v/v), the reaction flask was
removed from the cooling bath and stirred for another 15–20 min by which time a
123

B. Kumar et al.
Table 4 Reusability of NH2PhSO3H for the synthesis of 2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-
3-aryl-3-(arylamino) propan-1-ones using 10 mol% of the catalysta
Entry
Run number
Time (min)
Yield (%)
1
2
3
4
5
a
1
2
3
4
5
90
90
92
91
88
88
84
100
120
130
Reaction conditions: (40-hydroxy-30,50-dinitrophenyl) (3-aryloxiran-2-yl) methanone (0.02 mol), aro-
matic amine (0.02 mol) and sulfanilic acid (10 mol%) in dioxane (15 ml) at 90 °C temperature for 2 h
precipitate formed. The reaction mixture was vacuum-filtered followed by washing
with cold water, which afforded crude samples which, on recrystallization with
ethanol, gave purified products. Physical characterization data are as follows.
2a. (40-Hydroxy-30,50-dinitrophenyl) (3-phenyloxiran-2-yl) methanone
Yield (68 %); mp. 100–102 °C; IR (KBr): 3,568, 3,441, 2,935, 1,680, 1,525, 1,372,
1
1,070, 615 cm-1; H NMR (400 MHz, CDCl3): d = 11.20 (s, 1H, Ar–OH), 8.20
(m, 2H, Ar–H), 6.8–7.5 (m, 5H, Ar–H), 4.47 (d, aH, J = 1.60 Hz), 4.12 (d, bH,
J = 1.60 Hz) ppm; 13C NMR (100 MHz, CDCl3): d = 197.50, 151.90, 137.70,
136.40, 131.80, 130.34, 128.40, 137.70, 125.48, 66.10, 58.84. MS m/z 330.25 (M?).
Anal. calcd. for C15H10N2O7: C, 54.55; H, 3.05; N, 8.48 %. Found: C, 54.46; H,
2.95; N, 8.38 %.
2b. [3-(2-Chlorophenyl)oxiran-2-yl] (40-hydroxy-30,50-dinitrophenyl) methanone
Yield (65 %); mp. 142–144 °C; IR (KBr): 3,572, 3,456, 2,940, 1,682, 1,511, 1,370,
1
1,074, 840, 618 cm-1; H NMR (400 MHz, CDCl3): d = 11.15 (s, 1H, Ar–OH),
8.25 (m, 2H, Ar–H), 7.01–7.70 (m, 4H, Ar–H), 4.44 (d, aH, J = 1.60 Hz), 4.16 (d,
bH, J = 1.60 Hz) ppm; 13C NMR (100 MHz, CDCl3): d = 197.60, 151.40, 138.20,
136.45, 131.80, 130.71, 129.34, 128.81, 126.05, 68.10, 49.84. MS m/z 364.69 (M?).
Anal. calcd. for C15H9ClN2O7: C, 49.40; H, 2.49; N, 7.68 %. Found: C, 49.45; H,
2.58; N, 7.58 %.
2c. [3-(3-Chlorophenyl) oxiran-2-yl] (40-hydroxy-30,50-dinitrophenyl) methanone
Yield (67 %); mp. 130–132 °C; IR (KBr): 3,579, 3,452, 2,923, 1,684, 1,514, 1,376,
1
1,077, 845, 621 cm-1; H NMR (400 MHz, CDCl3): d = 11.26 (s, 1H, Ar–OH),
8.24 (m, 2H, Ar–H), 7.12–7.74 (m, 4H, Ar–H), 4.41 (d, aH, J = 1.70 Hz), 4.11 (d,
bH, J = 1.70 Hz) ppm; 13C NMR (100 MHz, CDCl3): d = 197.40, 151.48, 139.21,
136.48, 133.45, 131.41, 129.12, 128.88, 125.00, 123.45, 69.35, 57.70. MS m/
z 364.69 (M?). Anal. calcd. for C15H9ClN2O7: C, 49.40; H, 2.49; N, 7.68 %.
Found: C, 49.49; H, 2.55; N, 7.52 %.
123

Synthesis of some new substituted oxiranes
2d. [3-(4-Chlorophenyl) oxiran-2-yl] (40-hydroxy-30,50-dinitrophenyl) methanone
Yield (66 %); mp. 144–146 °C; IR (KBr): 3,564, 3,468, 2,936, 1,681, 1,521, 1,369,
1
1,074, 840, 623 cm-1; H NMR (400 MHz, CDCl3): d = 11.28 (s, 1H, Ar–OH),
8.22 (m, 2H, Ar–H), 7.10–7.70 (m, 4H, Ar–H), 4.48 (d, aH, J = 1.70 Hz), 4.16 (d,
bH, J = 1.70 Hz) ppm; 13C NMR (100 MHz, CDCl3): d = 197.41, 151.98, 136.99,
135.01, 133.06, 131.85, 128.88, 126.96, 69.14, 58.21. MS m/z 364.69 (M?). Anal.
calcd. for C15H9ClN2O7: C, 49.40; H, 2.49; N, 7.68 %. Found: C, 49.45; H, 2.58; N,
7.55 %.
2e. (40-Hydroxy-30,50-dinitrophenyl) [3-(4-methoxyphenyl)oxiran-2-yl] methanone
Yield (65 %); mp. 122–124 °C; IR (KBr): 3,575, 3,465, 2,948, 1,678, 1,525, 1,365,
1
1,121, 1,071, 618 cm-1; H NMR (400 MHz, CDCl3): d = 11.22 (s, 1H, Ar–OH),
8.18 (m, 2H, Ar–H), 7.08–7.56 (m, 4H, Ar–H), 4.56 (d, aH, J = 1.75 Hz), 4.16 (d,
bH, J = 1.75 Hz), 3.91 (s, 3H, Ar–OCH3) ppm; 13C NMR (100 MHz, CDCl3):
d = 197.58, 161.21, 151.56, 136.01, 131.15, 130.20, 126.51, 114.41, 69.32, 58.26,
56.23. MS m/z 360.28 (M?). Anal. calcd. for C16H12N2O8: C, 53.34; H, 3.36; N,
7.78 %. Found: C, 53.28; H, 3.30; N, 7.60 %.
2f. (40-Hydroxy-30,50-dinitrophenyl) [3-(3,4-dimethoxyphenyl) oxiran-2-yl]
methanone
Yield (62 %); mp. 135–137 °C; IR (KBr): 3,568, 3,470, 2,912, 1,676, 1,521, 1,360,
1,145, 1,121, 1,076, 626 cm-1; 1H NMR (400 MHz, CDCl3): d = 11.21 (s, 1H, Ar–
OH), 8.14 (m, 2H, Ar–H), 7.14–7.75 (m, 3H, Ar–H), 4.51 (d, aH, J = 1.65 Hz),
4.18 (d, bH, J = 1.65 Hz), 3.86 (2s, 6H, Ar–OCH3) ppm; 13C NMR (100 MHz,
CDCl3): d = 197.45, 151.14, 147.35, 136.74, 131.36, 118.32, 115.14, 112.85,
69.45, 58.56, 56.85. MS m/z 390.30 (M?). Anal. calcd. for C17H14N2O9: C, 52.31;
H, 3.62; N, 7.18 %. Found: C, 52.24; H, 3.52; N, 6.10 %.
2g. (40-Hydroxy-30,50-dinitrophenyl) [3-(3,4,5-trimethoxyphenyl) oxiran-2-yl]
methanone
Yield (67 %); mp. 145–147 °C; IR (KBr): 3,575, 3,474, 2,948, 1,671, 1,530, 1,358,
1,158, 1,136, 1,078, 621 cm-1; 1H NMR (400 MHz, CDCl3): d = 11.26 (s, 1H, Ar–
OH), 8.18 (m, 2H, Ar–H), 7.10–7.85 (m, 2H, Ar–H), 4.53 (d, aH, J = 1.60 Hz),
4.10 (d, bH, J = 1.60 Hz), 3.75 (3s, 9H, Ar–OCH3) ppm; 13C NMR (100 MHz,
CDCl3): d = 197.60, 151.58, 148.23, 132.15, 131.85, 104.37, 69.78, 58.54, 56.79.
MS m/z 420.33 (M?). Anal. calcd. for C18H16N2O10: C, 51.43; H, 3.84; N, 6.66 %.
Found: C, 51.35; H, 3.72; N, 6.54 %.
2h. (40-Hydroxy-30,50-dinitrophenyl) [3-(4-methylphenyl)oxiran-2-yl] methanone
Yield (65 %); mp. 156–158 °C; IR (KBr): 3,568, 3,441, 2,912, 2,978, 1,686, 1,532,
1
1,368, 1,076, 623 cm-1; H NMR (400 MHz, CDCl3): d = 11.25 (s, 1H, Ar–OH),
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B. Kumar et al.
8.22 (m, 2H, Ar–H), 6.80–7.72 (m, 4H, Ar–H), 4.47 (d, aH, J = 1.58 Hz), 4.21 (d,
bH, J = 1.58 Hz), 2.54 (s, 3H, Ar–CH3) ppm; 13C NMR (100 MHz, CDCl3):
d = 197.50, 151.52, 137.56, 136.56, 134.89, 131.34, 129.86, 125.52, 65.18, 58.14,
20.58. MS m/z 344.27 (M?). Anal. calcd. for C16H12N2O7: C, 55.82; H, 3.51; N,
8.14 %. Found: C, 55.75; H, 3.43; N, 8.02 %.
2i. [3-(2-Bromophenyl)oxiran-2-yl] (40-hydroxy-30,50-dinitrophenyl) methanone
Yield (61 %); mp. 110–112 °C; IR (KBr): 3,585, 3,445, 2,941, 1,675, 1,518, 1,377,
1
1,065, 848, 614 cm-1; H NMR (400 MHz, CDCl3): d = 11.25 (s, 1H, Ar–OH),
8.26 (m, 2H, Ar–H), 7.01–7.70 (m, 4H, Ar–H), 4.40 (d, aH, J = 1.71 Hz), 4.18 (d,
bH, J = 1.71 Hz) ppm; 13C NMR (100 MHz, CDCl3): d = 197.62, 151.40, 141.20,
136.12, 131.10, 130.14, 127.58, 120.89, 68.45, 50.84. MS m/z 409.15 (M?). Anal.
calcd. for C15H9BrN2O7: C, 44.03; H, 2.22; N, 6.85 %. Found: C, 43.92; H, 2.12; N,
6.72 %.
2j. [3-(4-Bromophenyl)oxiran-2-yl] (40-hydroxy-30,50-dinitrophenyl) methanone
Yield (62 %); mp. 124–126 °C; IR (KBr): 3,568, 3,448, 2,936, 1,678, 1,514, 1,368,
1
1,072, 886, 635 cm-1; H NMR (400 MHz, CDCl3): d = 11.34 (s, 1H, Ar–OH),
8.21 (m, 2H, Ar–H), 7.20–7.70 (m, 4H, Ar–H), 4.40 (d, aH, J = 1.55 Hz), 4.10 (d,
bH, J = 1.55 Hz) ppm; 13C NMR (100 MHz, CDCl3): d = 197.40, 151.48, 131.98,
127.56, 122.80, 65.68, 58.56. MS m/z 409.15 (M?). Anal. calcd. for C15H9BrN2O7:
C, 44.03; H, 2.22; N, 6.85 %. Found: C, 43.92; H, 2.12; N, 6.72 %.
General procedure for the synthesis of 2-hydroxy-1-(40-hydroxy-30,50-
dinitrophenyl)-3-aryl-3-(arylamino) propan-1-one derivatives (3a–o)
A mixture of 2 (0.02 mol), substituted aniline (0.02 mol) and sulfanilic acid
(10 mol%) in dioxane (15 ml) was stirred on a water bath for an appropriate time at
90 °C. After the completion of the reaction (monitored by TLC, eluent: benzene–
EtOAc 8:2 v/v), the mixture was cooled to room temperature and the catalyst was
removed by filtration. Removal of the solvent in vacuo afforded products 3a–o,
which were recrystallized from ethanol.
3a. 2-Hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-phenyl-3-[(3-methylphenyl)
amino] propan-1-one
mp. 145–147 °C; IR (KBr): 3,568, 3,448, 3,320, 2,936, 1,675, 1,514, 1,368,
1
635 cm-1; H NMR (400 MHz, CDCl3): d = 11.50 (s, 1H, Ar–OH), 8.61 (m, 2H,
Ar–H), 6.45–7.60 (m, 9H, Ar–H), 6.30 (br, s, 1H, –CH–OH), 5.60 (d, aH,
J = 2.10 Hz), 4.70 (d, bH, J = 2.10 Hz), 3.20 (s, 1H, –NH–), 2.33 (s, 3H, Ar–CH3)
ppm; 13C NMR (100 MHz, CDCl3): d = 197.20, 151.45, 143.25, 142.65, 138.80,
136.95, 131.65, 129.01, 128.98, 127.52, 126.50, 117.02, 113.85, 109.65, 90.50,
59.55, 20.20. MS m/z 437.40 (M?). Anal. calcd. for C22H19N3O7: C, 60.41; H, 4.38;
N, 9.61 %. Found: C, 60.51; H, 4.45; N, 9.70 %.
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Synthesis of some new substituted oxiranes
3b. 3-(200-Chlorophenyl)-2-hydroxyl-1-(40-hydroxy-30,50-dinitrophenyl)-3-[(3-
methylphenyl) amino] propan-1-one
mp. 168–170 °C; IR (KBr): 3,575, 3,440, 3,325, 2,938, 1,671, 1,512, 1,361, 784,
1
630 cm-1; H NMR (400 MHz, CDCl3): d = 11.45 (s, 1H, Ar–OH), 8.60 (m, 2H,
Ar–H), 6.50–7.60 (m, 8H, Ar–H), 6.32 (br, s, 1H, –CH–OH), 5.56 (d, aH,
J = 2.15 Hz), 4.64 (d, bH, J = 2.15 Hz), 3.22 (s, 1H, –NH–), 2.30 (s, 3H, Ar–CH3)
ppm; 13C NMR (100 MHz, CDCl3): d = 197.45, 151.23, 143.25, 142.00, 138.85,
136.95, 132.70, 131.05, 129.90, 128.51, 127.02, 126.91, 117.20, 113.20, 109.22,
89.56, 50.54, 20.35. MS m/z 471.85 (M?). Anal. calcd. for C22H18ClN3O7: C,
56.00; H, 3.85; N, 8.91 %. Found: C, 55.88; H, 3.76; N, 8.85 %.
3c. 3-(300-Chlorophenyl)-2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-[(3-
methylphenyl) amino] propan-1-one
mp. 162–164 °C; IR (KBr): 3,571, 3,455, 3,335, 2,954, 1,670, 1,518, 1,360, 780,
1
638 cm-1; H NMR (400 MHz, CDCl3): d = 11.41 (s, 1H, Ar–OH), 8.62 (m, 2H,
Ar–H), 6.50–7.65 (m, 8H, Ar–H), 6.25 (br, s, 1H, –CH–OH), 5.50 (d, aH,
J = 2.50 Hz), 4.60 (d, bH, J = 2.50 Hz), 3.25 (s, 1H, –NH–), 2.31 (s, 3H, Ar–CH3)
ppm; 13C NMR (100 MHz, CDCl3): d = 197.01, 151.34, 143.21, 138.15, 136.46,
133.95, 131.75, 129.02, 127.94, 126.55, 125.24, 120.24, 117.85, 113.10, 109.54,
90.66, 58.85, 20.30. MS m/z 471.85 (M?). Anal. calcd. for C22H18ClN3O7: C,
56.00; H, 3.85; N, 8.91 %. Found: C, 55.88; H, 3.76; N, 8.85 %.
3d. 3-(400-Chlorophenyl)-2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-[(3-
methylphenyl)amino] propan-1-one
mp. 125–127 °C; IR (KBr): 3,576, 3,458, 3,348, 2,932, 1,674, 1,524, 1,362, 783,
1
635 cm-1; H NMR (400 MHz, CDCl3): d = 11.43 (s, 1H, Ar–OH), 8.64 (m, 2H,
Ar–H), 6.52–7.65 (m, 8H, Ar–H), 6.25 (br, s, 1H, –CH–OH), 5.53 (d, aH,
J = 2.00 Hz), 4.62 (d, bH, J = 2.00 Hz), 3.23 (s, 1H, –NH–), 2.34 (s, 3H, Ar–CH3)
ppm; 13C NMR (100 MHz, CDCl3): d = 197.26, 151.36, 143.25, 140.25, 138.75,
131.90, 129.65, 128.14, 117.95, 113.51, 109.21, 90.45, 59.65, 20.45. MS m/z 471.85
(M?). Anal. calcd. for C22H18ClN3O7: C, 56.00; H, 3.85; N, 8.91 %. Found: C,
55.88; H, 3.76; N, 8.85 %.
3e. 2-Hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-(400-methoxyphenyl)-3-[(3-
methylphenyl) amino] propan-1-one
mp. 148–150 °C; IR (KBr): 3,577, 3,468, 3,375, 2,940, 1,675, 1,530, 1,365, 1,118,
1
638 cm-1; H NMR (400 MHz, CDCl3): d = 11.40 (s, 1H, Ar–OH), 8.61 (m, 2H,
Ar–H), 6.55–7.68 (m, 8H, Ar–H), 6.20 (br, s, 1H, –CH–OH), 5.51 (d, aH,
J = 2.10 Hz), 4.60 (d, bH, J = 2.10 Hz), 3.70 (s, 3H, Ar–OCH3), 3.21 (s, 1H, –
NH–), 2.31 (s, 3H, Ar–CH3) ppm; 13C NMR (100 MHz, CDCl3): d = 197.28,
160.32, 151.45, 143.22, 138.85, 136.91, 134.60, 131.05, 129.89, 128.50, 117.00,
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B. Kumar et al.
113.95, 109.25, 90.45, 59.56, 56.32, 20.25. MS m/z 467.43 (M?). Anal. calcd. for
C23H21N3O8: C, 59.10; H, 4.53; N, 9.00 %. Found: C, 59.02; H, 4.44; N, 8.88 %.
3f. 2-Hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-(300,400-dimethoxyphenyl)-3-[(3-
methylphenyl)amino] propan-1-one
mp. 122–124 °C; IR (KBr): 3,586, 3,472, 3,366, 2,949, 1,674, 1,541, 1,360, 1,148,
1
1,110, 641 cm-1; H NMR (400 MHz, CDCl3): d = 11.55 (s, 1H, Ar–OH), 8.66
(m, 2H, Ar–H), 6.55–7.65 (m, 7H, Ar–H), 6.36 (br, s, 1H, –CH–OH), 5.55 (d, aH,
J = 2.15 Hz), 4.55 (d, bH, J = 2.15 Hz), 3.65 (2s, 6H, Ar–OCH3), 3.25 (s, 1H, –
NH–), 2.25 (s, 3H, Ar–CH3) ppm; 13C NMR (100 MHz, CDCl3): d = 197.52,
151.02, 147.46, 145.45, 143.85, 138.91, 135.48, 131.01, 129.85, 120.58, 117.02,
114.98, 113.88, 112.20, 109.85, 90.50, 59.75, 56.25, 20.85. MS m/z 497.45 (M?).
Anal. calcd. for C24H23N3O9: C, 57.95; H, 4.66; N, 8.45 %. Found: C, 57.85; H,
4.53; N, 8.32 %.
3g. 2-Hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-(300,400,500-trimethoxyphenyl)-3-
[(3-methylphenyl) amino] propan-1-one
mp. 155–157 °C; IR (KBr): 3,565, 3,465, 3,375, 2,958, 1,675, 1,548, 1,364, 1,165,
1
1,135, 1,115, 651 cm-1; H NMR (400 MHz, CDCl3): d = 11.45 (s, 1H, Ar–OH),
8.55 (m, 2H, Ar–H), 6.65–7.60 (m, 6H, Ar–H), 6.35 (br, s, 1H, –CH–OH), 5.52 (d,
aH, J = 2.35 Hz), 4.45 (d, bH, J = 2.35 Hz), 3.45 (3s, 9H, Ar–OCH3), 3.30 (s, 1H,
–NH–), 2.36 (s, 3H, Ar–CH3) ppm; 13C NMR (100 MHz, CDCl3): d = 197.78,
151.00, 148.85, 143.40, 138.45, 136.98, 131.55, 129.00, 117.85, 113.25, 109.05,
106.65, 90.65, 60.30, 56.85, 20.95. MS m/z 527.48 (M?). Anal. calcd. for
C25H25N3O10: C, 56.92; H, 4.78; N, 7.97 %. Found: C, 56.85; H, 4.65; N, 7.85 %.
3h. 2-Hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-(400-methylphenyl)-3-[(3-
methylphenyl)amino] propan-1-one
mp. 136–138 °C; IR (KBr): 3,570, 3,435, 3,356, 2,970, 1,670, 1,519, 1,361, 685,
1
635 cm-1; H NMR (400 MHz, CDCl3): d = 11.50 (s, 1H, Ar–OH), 8.65 (m, 2H,
Ar–H), 6.40–7.65 (m, 8H, Ar–H), 6.31 (br, s, 1H, –CH–OH), 5.58 (d, aH,
J = 2.15 Hz), 4.25 (d, bH, J = 2.15 Hz), 3.20 (s, 1H, –NH–), 2.65 (s, 3H, Ar–
CH3), 2.33 (s, 3H, Ar–CH3) ppm; 13C NMR (100 MHz, CDCl3): d = 197.20,
151.45, 143.20, 139.60, 138.80, 136.90, 135.95, 131.25, 129.98, 127.75, 117.15,
113.85, 109.12, 90.32, 59.55, 20.51. MS m/z 451.43 (M?). Anal. calcd. for
C23H21N3O7: C, 61.19; H, 4.69; N, 9.31 %. Found: C, 61.11; H, 4.54; N, 9.22 %.
3i. 3-(200-Bromophenyl)-2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-[(3-
methylphenyl) amino] propan-1-one
mp. 140–142 °C; IR (KBr): 3,571, 3,465, 3,341, 2,972, 1,677, 1,511, 1,355, 850,
631 cm-1; 1H NMR (400 MHz, CDCl3): d = 11.41 (s, 1,H, Ar–OH), 8.60 (m, 2H,
Ar–H), 6.35–7.60 (m, 8H, Ar–H), 6.20 (br, s, 1H, –CH–OH), 5.45 (d, aH,
123

Synthesis of some new substituted oxiranes
J = 2.30 Hz), 4.56 (d, bH, J = 2.30 Hz), 3.28 (s, 1H, –NH–), 2.30 (s, 3H, Ar–CH3)
ppm; 13C NMR (100 MHz, CDCl3): d = 197.45, 151.45, 145.32, 143.15, 138.46,
136.15, 131.95, 128.15, 127.95, 121.05, 117.85, 113.45, 109.24, 85.34, 51.85,
20.90. MS m/z 516.30 (M?). Anal. calcd. for C22H18BrN3O7: C, 51.18; H, 3.51; N,
8.14 %. Found: C, 51.06; H, 3.38; N, 8.04 %.
3j. 3-(400-Bromophenyl)-2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-[(3-
methylphenyl) amino] propan-1-one
mp. 102–104 °C; IR (KBr): 3,585, 3,472, 3,354, 2,965, 1,670, 1,525, 1,370, 856,
1
638 cm-1; H NMR (400 MHz, CDCl3): d = 11.60 (s, 1H, Ar–OH), 8.52 (m, 2H,
Ar–H), 6.45–7.66 (m, 8H, Ar–H), 6.25 (br, s, 1H, –CH–OH), 5.44 (d, aH,
J = 2.25 Hz), 4.50 (d, bH, J = 2.25 Hz), 3.22 (s, 1H, –NH–), 2.35 (s, 3H, Ar–CH3)
ppm; 13C NMR (100 MHz, CDCl3): d = 197.95, 151.12, 143.58, 141.45, 138.95,
136.45, 129.85, 117.05, 113.95, 109.85, 90.35, 59.25, 20.54. MS m/z 516.30 (M?).
Anal. calcd. for C22H18BrN3O7: C, 51.18; H, 3.51; N, 8.14 %. Found: C, 51.06; H,
3.38; N, 8.04 %.
3k. 2-Hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-phenyl-3-(phenylamino)propan-
1-one
mp. 130–132 °C; IR (KBr): 3,570, 3,480, 3,325, 2,940, 1,675, 1,519, 1,360, 630 cm-1
;
1H NMR (400 MHz, CDCl3): d = 11.55 (s, 1H, Ar–OH), 8.60 (m, 2H, Ar–H),
6.50–7.55(m, 10H, Ar–H), 6.32(br, s, 1H, –CH–OH), 5.60(d, aH,J = 2.1 Hz), 4.75(d,
bH, J = 2.1 Hz), 3.25 (s, 1H, –NH–) ppm; 13C NMR (100 MHz, CDCl3): d = 197.24,
151.45, 143.20, 142.65, 136.00, 131.15, 129.85, 128.01, 127.98, 126.50, 116.02, 112.85,
90.45, 59.65. MS m/z 423.37 (M?). Anal. calcd. for C21H17N3O7: C, 59.57; H, 4.05; N,
9.92 %. Found: C, 59.45; H, 3.95; N, 9.85 %.
3l. 2-Hydroxy-1-(4-hydroxy-3,5-dinitrophenyl)-3-[(3-nitrophenyl)amino]-3-
phenylpropan-1-one
mp. 165–167 °C; IR (KBr): 3,580, 3,471, 3,332, 2,940, 1,672, 1,520, 1,495, 1,360,
1
1,358, 642 cm-1; H NMR (400 MHz, CDCl3): d = 11.70 (s, 1H, Ar–OH), 8.62
(m, 2H, Ar–H), 6.75–7.85 (m, 9H, Ar–H), 6.30 (br, s, 1H, –CH–OH), 5.62 (d, aH,
J = 2.10 Hz), 4.70 (d, bH, J = 2.10 Hz), 3.15 (s, 1H, –NH–) ppm; 13C NMR
(100 MHz, CDCl3): d = 197.15, 151.45, 149.50, 144.40, 142.65, 136.15, 131.05,
130.40, 128.70, 127.75, 126.90, 118.10, 112.75, 107.25, 90.20, 59.35. MS m/
z 468.37 (M?). Anal. calcd. for C21H16N4O9: C, 53.85; H, 3.44; N, 11.96 %. Found:
C, 53.73; H, 3.36; N, 11.85 %.
3m. 2-Hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-(300,400-dimethoxyphenyl)-3-
[(3-nitrophenyl) amino] propan-1-one
mp. 156–158 °C; IR (KBr): 3,574, 3,485, 3,372, 2,952, 1,673, 1,548, 1,360, 1,340,
1,165, 1,148, 1,118, 640 cm-1; 1H NMR (100 MHz, CDCl3): d = 11.52 (s, 1H, Ar–
123

B. Kumar et al.
OH), 8.60 (m, 2H, Ar–H), 6.70–7.85 (m, 7H, Ar–H), 6.40 (br, s, 1H, –CH–OH),
5.50 (d, aH, J = 2.15 Hz), 4.52 (d, bH, J = 2.15 Hz), 3.62 (2s, 6H, Ar–OCH3),
3.30 (s, 1H, –NH–) ppm; 13C NMR (100 MHz, CDCl3): d = 197.52, 151.02,
149.25, 147.40, 145.55, 144.25, 136.90, 135.70, 131.15, 130.90, 120.65, 118.10,
114.15, 113.94, 112.85, 107.20, 90.70, 59.10, 56.65. MS m/z 528.42 (M?). Anal.
calcd. for C23H20N4O11: C, 52.38; H, 3.81; N, 10.60 %. Found: C, 52.29; H, 3.72;
N, 10.46 %.
3n. 3-[(3-Bromophenyl)amino]-2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-
(300,400-dimethoxyphenyl)-3-propan-1-one
mp. 105–107 °C; IR (KBr): 3,578, 3,488, 3,368, 2,948, 1,670, 1,548, 1,342, 1,165,
1
1,124, 885, 655 cm-1; H NMR (400 MHz, CDCl3): d = 11.50 (s, 1H, Ar–OH),
8.66 (m, 2H, Ar–H), 6.60–7.75 (m, 7H, Ar–H), 6.41 (br, s, 1H, –CH–OH), 5.55 (d,
aH, J = 2.15 Hz), 4.48 (d, bH, J = 2.15 Hz), 3.65 (2s, 6H, Ar–OCH3), 3.34 (s, 1H,
–NH–) ppm; 13C NMR (100 MHz, CDCl3): d = 197.85, 151.45, 147.75, 145.30,
136.90, 135.68, 131.12, 123.90, 120.68, 115.45, 114.40, 113.40, 111.81, 90.55,
59.60, 56.45. MS m/z 562.32 (M?). Anal. calcd. for C23H20BrN3O9: C, 49.12; H,
3.58; N, 7.47 %. Found: C, 49.01; H, 3.46; N, 7.35 %.
3o. 3-(200-Bromophenyl)-2-hydroxy-1-(40-hydroxy-30,50-dinitrophenyl)-3-[(3-
nitrophenyl) amino] propan-1-one
mp. 144–146 °C; IR (KBr): 3,576, 3,455, 3,350, 2,967, 1,672, 1,512, 1,498, 1,355,
1
1,346, 858, 642 cm-1; H NMR (400 MHz, CDCl3): d = 11.48 (s, 1H, Ar–OH),
8.56 (m, 2H, Ar–H), 6.45–7.65 (m, 8H, Ar–H), 6.25 (br, s, 1H, –CH–OH), 5.40 (d,
aH, J = 2.30 Hz), 4.52 (d, bH, J = 2.30 Hz), 3.35 (s, 1H, –NH–) ppm; 13C NMR
(100 MHz, CDCl3): d = 197.40, 151.45, 149.30, 145.35, 144.10, 136.46, 131.56,
130.90, 129.30, 128.91, 127.65, 121.15, 118.80, 112.55, 107.45, 89.60, 51.55. MS
m/z 547.27 (M?). Anal. calcd. for C21H15BrN4O9: C, 46.09; H, 2.76; N, 10.24 %.
Found: C, 45.96; H, 2.66; N, 10.12 %.
Acknowledgments The authors are thankful to Prof. B.L. Verma, Retd. Professor of Chemistry, M.L.S.
University Udaipur and Dr. S. Jakhoria, Dean, FASC, MITS University, for their constant encouragement
during this work. The authors are also grateful to the Head, Sophisticated Analytical Instrument Facility,
Panjab University, Chandigarh, for spectral analyses.
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