An efficient synthesis of 5-benzoyloxazolines by regio- and stereo-controlled reaction of N-substituted 2-benzoylaziridines under microwave irradiation

Article abstract of DOI:10.1002/jhet.5570450632

(Chemical Equation Presented) Several N-acyl-2-benzoylaziridines were prepared conveniently in good to high yields (71-93%) and used in the preparation of 5-benzoyloxazolines (76-91%) by a regio- and stereo-controlled reaction in the presence of NaI as an

Full text of DOI:10.1002/jhet.5570450632

Nov-Dec 2008
1765
An Efficient Synthesis of 5-Benzoyloxazolines by Regio- and
Stereo-controlled Reaction of N-Substituted 2-Benzoylaziridines
Under Microwave Irradiation
Heshmat A. Samimi, Manouchehr Mamaghani* and Khalil Tabatabaeian
Department of Chemistry, Faculty of Sciences, University of Guilan, P. O. Box 41335-1914, Rasht, Iran
m-chem41@guilan.ac.ir
Received October 24, 2007
R2
R2
O
NH
N
O
N
CH2Cl2
NaI/ CH3CN
O
R1
O
O
R2COCl/Et3N
MW (260 W)
R1
R1
Ph
Ph
Ph
1
2a-i
4a-i
R1= C6H5, 3-NO2C6H4; R2= CH3, C6H5, 3-NO2C6H4, 2-furyl, C6H5CH=CH, 2-ClC6H4
Several N-acyl-2-benzoylaziridines were prepared conveniently in good to high yields (71-93%) and
used in the preparation of 5-benzoyloxazolines (76-91%) by a regio- and stereo-controlled reaction in the
presence of NaI as an efficient catalyst under microwave irradiation in short reaction times (5-10 mins).
The structure of the regioisomeric product was confirmed by X-ray analysis.
J. Heterocyclic Chem., 45, 1765 (2008).
INTRODUCTION
such as CoCl2 [11b], HClO4 [11c], TMS-CN [11d], SiF4
[11e] and Cl3CCN/DBU [11f] have been employed to
generate the oxazolines from an epoxide.
Another useful method for the preparation of
oxazolines is the application of aziridines [12]. Through
ring expansion, aziridines also provide oxazolines [13-
16].
The oxazoline ring system has been known for more
than a century and constitutes an important class of
compounds that has attracted scientists from various areas
due to its unique properties and capacity to serve as a
synthetic precursor or mediator in a multitude of chemical
processes [1].
The ring expansion of aziridines into oxazolines,
induced by iodide, was first discovered by Heine [17a]
and for some aziridines Cardillo’s group reported that
aziridines undergo a ring expansion into oxazolines in the
presence of BF3.OEt2 [18]. Recently this reaction was
employed in the ring expansion reaction of aziridine 2-
carboxylic ester into oxazolines in a regio- and stereo-
controlled manner [17b].
Despite the vast amount of work reported on the
synthesis and reactivity of aziridines in general and
aziridines carboxylic esters [12d,19-21], in particular,
further developments in the synthesis and utilization of
aziridines as useful synthetic precursors is still required.
In continuation of our recent interest in the synthesis
and use of N-heterocyclic compounds in organic synthesis
[22], herein we report the synthesis of N-acyl-2-
benzoylaziridines and their application in a regio- and
stereo-controlled reaction for the preparation of some
trans-5-benzoyloxazolines under microwave condition in
high yields and short reaction times (5-10 mins).
In recent years, oxazolines with various backbones have
found widespread use in asymmetric reactions as valuable
chiral auxiliaries [2] and versatile intermediates in P-C
bond formation [3a] and in the synthesis of ꢀ-substituted
serines because of their utility in the synthesis of various
antibiotics [3b]. Substituted oxazoline derivatives
prepared stereospecifically were used in the synthesis of
naturally occurring non-proteinogenic ꢀ-hydroxy-ꢀ-
amino acids [4] and as starting material in the synthesis of
the neurotrophic factor Lactacystin [5,6]. Among the
oxazoline derivatives, bis-oxazolines have been employed
as suitable ligands in the asymmetric catalysis of organic
reactions [7]. Moreover a great number of oxazolines with
biological activity have been isolated from marine
organisms [8].
Several synthetic methods have been described for the
synthesis of oxazolines [9,1a]. In most cases they are
prepared from amino alcohols [7b]. Some other methods
using carboxylic esters, nitriles or aldehydes as starting
materials have also been described but most of them use
strongly acidic conditions or stringent reaction parameters
[10]. Methods using strained-ring opening reactions have
also been developed. In an interesting acid-catalyzed
(BF3.OEt2) ring-opening approach glycidyl tosylate in the
presence of acetonitrile has provided oxazolines in a
Ritter-type reaction in high yield [11a]. Other reagents
RESULTS AND DISCUSSION
At the outset of this study trans-2-benzoylaziridine 1
was prepared via Gabriel-Cromwell procedure [23], by
bromination of the related ꢀ,ꢁ-unsaturated carbonyl
compounds, followed with the reaction of ammonia
solution (30%) in methanol at room temperature. trans-2-

1766
H. A. Samimi, M. Mamaghani and K. Tabatabaeian
Vol 45
Benzoylaziridine 1 was used for the preparation of N-
acetyl-2-benzoylaziridine (2a) in the presence and
absence of Et3N (Scheme 1).
acylation of 2-benzoylaziridines (1) in the presence of
Et3N.
All the synthesized 2-benzoylaziridines were used in a
ring expansion reaction for preparation of the related
5-benzoyloxazolines under microwave irradiation
(260 W) (Scheme 2).
Scheme 1
R2OCHN
H
O
Scheme 2
R1
H
l
C
Cl
R2
O
R2
CO
H
2
R
3
Ph
Cl2
N
CH2
NaI
CH CN
3
/
N
N
O
O
HCl/THF
Na2CO3/THF
R1
R
O
2 COCl
MW (260 W)
R1
O
Ph
R1
/
E
1
t
CH
2 Cl
R2
O
3 N
Ph
Ph
2
2a-i
4a-i
N
O
R1
In this study we initially used ring expansion of
2-benzoylaziridines 2b as a model reaction to investigate
the effect of different catalysts on the efficiency of this
reaction. The results of this study revealed that the ring
expansion reaction in the presence of Cu(OTf)2,
BF3.OEt2, MgBr2, or ZnCl2 (20 mol% catalyst) gave a
mixture of products with only a small amount (10-18%)
of the desired oxazoline (4b), while with TiCl4 a moderate
yield (65%) was obtained. However the best result was
achieved with NaI (90% yield) and the ring expansion of
all the synthesized 2-benzoylaziridines (2a-i) to the
Ph
2
The reaction in the absence of Et3N afforded 3a by
chloride attack on C2 position of aziridine ring. In a
separate experiment a sample of 2a was treated with HCl
in THF which afforded 3a in 72%. Reconversion of this
product (3a) into 2a was carried out by using
Na2CO3/THF which furnished 2a in a clean reaction in
95% yield. Therefore preparation of N-substituted
2-benzoylaziridines (2) (Table 1) was conducted by
Table 1
Preparation of N-substituted 2-benzoylaziridines (2a-i).
entry
R1
R2
Time (h)
yield (%)b
mp (ºC)
a
C6H5
C6H5
CH3
3
6
76c
93
92-94
86-88
b
C6H5
c
d
e
f
g
h
i
3-NO2C6H4
C6H5
3-NO2C6H4
3-NO2C6H4
C6H5
CH3
3-NO2C6H4
C6H5
4
5
6
5
4
4
6
71c
88
91
83
89
81
86
98-100
125-127
129-130
132-134
119-122
138-140
139-140
3-NO2C6H4
C4H3O
3-NO2C6H4
C6H5
C6H5CH=CH
2-ClC6H4
a All products were characterized by IR, NMR and elemental analysis. b Isolated yield. c As a mixture with 3 (~15% ).
Table 2
Microwave-assisted ring expansion of N-substituted 2-benzoylaziridines 2 into 5-benzoyloxazolines 4.
entry
R1
R2
Time (min)
yield (%)b
a
b
c
d
e
f
g
h
i
C6H5
C6H5
CH3
C6H5
8
8
78c
90
77
86
79
81
84
76
91
3-NO2C6H4
C6H5
CH3
10
7
3-NO2C6H4
C6H5
3-NO2C6H4
3-NO2C6H4
C6H5
5
3-NO2C6H4
2-furyl
8
5
3-NO2C6H4
C6H5CH=CH
2-ClC6H4
5
C6H5
1
10
a All products were characterized by IR, H NMR, 13C NMR and elemental analysis. b Isolated yield. CRing expansion of 2a (1.0 mmole) in
CH3CN (15 ml) in the presence of NaI (0.2 mmole) under reflux condition after 5 hours, produced 4a in 75%

Nov-Dec 2008
An Efficient Synthesis of 5-Benzoyloxazolines by Regio- and Stereo-controlled
1767
EXPERIMENTAL
related 5-benzoyloxazolines was performed in the
presence of NaI (20 mol%), furnishing the desired product
in good to high yields (76-91%) (Table 2).
1H NMR spectra were obtained on a Bruker DRX-500 and
those of 13C NMR spectra on a Bruker DRX-125 Avance
spectrometer. FTIR spectra were recorded on a Shimadzu FTIR-
8400S spectrometer. Chemical shifts of 1H and 13C NMR spectra
are expressed in ppm downfield from tetramethylsilane. Melting
The formation of oxazoline 4 can be visualized by an
initial ring opening of the N-acylaziridine by the attack of
iodide ion (Scheme 3).
Scheme 3
R2
R2
O
N
O
N
N
H
O
O
R2
O
R1
H
N
O
O
R1
oute A
s
I
I
R
n
io
Ph
N
5
Ph
nver
O
R1
O
R2
R
R1
out
R2
Ph
e
B
inv
Ph
e
r
N
O
s
i
1
2
o
n
O
H
R1
Ph
H
R1
I
Ph
4
According to the mechanism presented in Scheme 3, in
the ring opening by nucleophilic addition of iodide, there are
two possible routes for oxazoline formation. In route A the
oxazoline with the nitrogen adjacent to the carbonyl group
will be formed, whereas route B will lead to the oxazoline
product with the oxygen adjacent to the carbonyl group. The
regioselectivity entirely depends on the stereo-electronic
nature of the substituents. In most of the reactions of this
type ring opening takes place in the less hindered position of
ring carbons [12f,15,16e,17, 21,24]. Since the spectral data
(e.g., nmr, ir, and elemental analysis) were not conclusive,
X-ray crystallographic analysis [25] was conducted on 4i to
verify product structure. As shown in Figure 1, path B
prevail to produce the product. In this pathway the aroyl
moiety at position 2 make it a suitable position for
nucleophilic attack.
In addition, the reaction takes place via a double
inversion, consequently a retention of configuration
occurs at the carbon atom bearing the aroyl group.
Figure 1. ORTEP plots of 4i (C22H16ClNO2).
5-Benzoyloxazolines
4 were obtained through ring
expansion of 2 in the presence of NaI in acetonitrile under
microwave irradiation (260 W) via a nucleophilic ring
opening by iodine and intra-nucleophilic attack of
oxygen, subsequently leading to a net retention of
configuration in two ring carbons. The result of X-ray
analysis clearly confirms the stereo-controlling nature of
this reaction.
In conclusion this work describes an efficient synthesis
of trans-5-benzoyloxazolines by the ring expansion of
trans-N-acyl-2-benzoylaziridines in a completely regio-
and stereo-controlled reaction in the presence of NaI
under microwave condition in short reaction time, which
pave the way for further functionalization of the oxazoline
skeleton. The research in this respect is under way.
points were measured on
a Buchi melting point B-540
instrument and are uncorrected. Elemental analyses were made
by a Carlo-Erba EA1110CNNO-S analyzer and agreed with the
calculated values. All the chemicals were purchased from Merck
and used without further purification.
General Procedure for Preparation of 2-Benzoylaziridines
(2a-i). Acyl chloride (1.0 mmole) was added dropwise to a
solution of aziridines (1) (1.0 mmole) and triethylamine (2.0
mmoles) in CH2Cl2 (10 mL) at 0 ºC. The mixture was stirred for
1 h at this temperature, 3-5 hours at room temperature and then
rinsed twice with water. The organic layer was dried over
anhydrous Na2SO4 and concentrated under reduced pressure.
The crude product was purified by column chromatography
(silica gel, EtOAc/Hexane: 2/5) to provide the desired keto-
aziridine 2 (71-93 %) (Table 1).

1768
H. A. Samimi, M. Mamaghani and K. Tabatabaeian
Vol 45
Preparation of N-((R)-2-Chloro-1,3-diphenyl-1-oxo-prop-
1418, 1236, 1060, 761 cm-1; 1H nmr (deuteriochloroform): ꢀ
5.50 (d, 1H, J = 6.5 Hz), 5.70 (d, 1H, J = 6.5 Hz), 7.3-7.7 (m,
11H), 7.9 (d, 2H, J = 7.3 Hz); 8.1 (d, 2H, J = 7.2); 13C nmr
(deuteriochloroform): ꢀ 74.06, 87.23, 127.38, 127.48, 128.60,
128.88, 129.17, 129.25, 129.41, 129.54, 132.28, 134.43, 134.63,
141.51, 164.25, 194.91; Anal. Calcd. for C22H17NO2 (327.13): C,
80.73; H, 5.20; N, 4.28. found: C, 80.70; H, 5.27; N, 4.33.
trans-1-Acyl-2-benzoyl-3-(3-nitrophenyl)aziridine (2c).
White solid, mp 98-100°C; ir (potassium bromide): 3048, 2993,
1676, 1592, 1532, 1356, 1430 cm-1; 1H nmr (deuterio-
chloroform): ꢀ 2.25 (s, 3H), 3.91 (d, 1H, J = 2.1 Hz), 4.2 (d, 1H,
J = 2.1 Hz), 7.2-7.8 (m, 5H), 8.0 (d, 2H, J = 7.3 Hz), 8.21 (d, 1H,
J = 7.3 Hz), 8.21 (s, 1H); 13C nmr (deuteriochloroform): ꢀ 20.9,
46.8, 48.1, 119.4, 123.2, 128.7, 129.5, 133.1, 134.1, 136.8,
139.2, 148.2, 173, 196; Anal. Calcd. for C17H14N2O4 (310.1): C,
65.81; H, 4.52; N, 9.03. found: C, 65.79; H, 4.57; N, 9.10.
trans-5-Benzoyl-2-methyl-4-(3-nitrophenyl)-2-oxazoline
(4c). Yellow solid, mp 85-88°C; ir (potassium bromide): 3068,
an-2-yl)acetamide (3a). From trans-1-Acyl-2-benzoyl-3-
phenylaziridine (2a). A mixture of 2a (1.0 mmole), 5 mL HCl
(0.5 M) in 15 mL THF/H2O (2:1; v/v) was stirred at room
temperature and the progress of the reaction was monitored by
TLC. After 3 hours, ethyl acetate (15 mL) and a 10% solution of
Na2CO3 (30 mL) was added. The organic layer was separated,
washed with water twice and dried over MgSO4. The organic
phase was separated and evaporated under reduced pressure. The
residue was purified by column chromatography (silica gel,
hexane-EtOAc: 4/1) to afford pure 3a (72%), mp 88-91 ºC.
Preparation of trans-1-Acetyl-2-benzoyl-3-phenylaziridine
(2a) From N-((R)-2-chloro-1,3-diphenyl-1-oxo-propan-2-yl)-
acetamide (3a). A mixture of 3a (1.0 mmole) and Na2CO3 (5.0
mmoles) was added to 15 mL THF/H2O (2:1, v/v) and the
reaction mixture was stirred at room temperature. The progress
of the reaction was monitored by TLC. When all of the 3a was
consumed (5 hours), ethyl acetate (15 mL) was added and the
organic layer was separated and washed with water. The organic
phase was dried over MgSO4 and the solvent was evaporated in
vacuo to afford keto-aziridine 2a in 95% yield.
General Procedure for the Preparation of 5-Benzoyl-
oxazolines (4a-i) Under Microwave Irradiation. Sodium
iodide (0.2 mmole) was added into a solution of 2 (1.0 mmole)
in CH3CN (15 mL) and the mixture was heated under
microwave irradiation (power 260 W) for 5-10 minutes. The
progress of the reaction was monitored by TLC (EtOAc-Hexane:
1/4)). After completion of the reaction, organic layer was rinsed
twice with water and dried with anhydrous Na2SO4. Evaporation
of the solvent under reduced pressure and subsequent
purification of the residue by column chromatography (silica
gel, EtOAc-Hexane: 1/4) provided 5-benzoyloxazoline 4 (76-
91%) (Table 2).
1
2996, 1688, 1535, 1354, 1237, 1052, 758, 691 cm-1; H nmr
(deuteriochloroform): ꢀ 2.01 (s, 3H), 5.6 (d, 1H, J = 7.2 Hz), 5.8
(d, 1H, J = 7.2 Hz), 7.34 (m, 3H), 7.45 (d, 1H, J = 7.7 Hz), 7.47
(m 1H), 7.5 (d, 1H, J = 8.0 Hz), 7.8 (d, 2H, J = 7.8 Hz), 8.1 (d,
1H, J = 7.8 Hz), 8.2 (s, 1H).13C nmr (CDCl3): ꢀ 21.2, 75.2, 77.8,
120.0, 122.4, 128.7, 128.8, 129.9, 133.2, 133.3, 136.8, 148.6,
168, 197; Anal. Calcd. for C17H14N2O4 (310.1): C, 65.81; H,
4.52; N, 9.03. found: C, 65.70; H, 4.65; N, 9.13.
trans-2-Benzoyl-1-(3-nitrobenzoyl)-3-phenylaziridine (2d).
White solid,mp 125- 127 °C; ir (potassium bromide): 3058, 188,
1580, 1530, 1354, 1175, 735, 691 cm-1; 1H nmr (deuteriochloro-
form): ꢀ 4.1 (d, 1H, J = 2.3 Hz), 4.3 (d, 1H, J = 2.3 Hz), 7.3 (dd,
2H, J = 6.9, 7.9 Hz), 7.6 (m, 3H), 7.7 (dd, 2H, J = 2.0, 7.6 Hz),
7.8 (d, 1H, J = 7.6 Hz), 7.9 (dd, 2H, J = 1.4, 8.9 Hz), 8.0 (dd,
2H, J =1.3, 8.6 Hz), 8.2-8.3 (m, 1H), 8.4 (dd, 1H, J = 1.5, 3.2
Hz). 13C nmr (deuteriochloroform): ꢀ 46.0, 49.0, 119.0, 123.2,
126.7, 127.2, 128.1, 128.7, 128.8, 129.5, 131.0, 133.1, 134.2,
136.8, 139.2, 148.1, 172.5, 195.1; Anal. Calcd for C22H16N2O4
(372.11): C, 70.97; H, 4.30; N, 7.53. found: C, 71.30; H, 4.36;
N, 7.59.
trans-1-Acetyl-2-benzoyl-3-phenylaziridine (2a). White
solid, mp 92-94°C; ir (potassium bromide): 3051, 1678, 1595,
1
1430, 1315 cm-1; H nmr (deuteriochloroform): ꢀ 2.27 (s, 3H),
3.9 (d, 1H, J = 2.1 Hz), 4.2 (d, 1H, J = 2.1 Hz,), 7.2-7.5 (m, 5H),
7.6-7.8 (m, 3H), 8.0 (d, 2H, J = 7.4 Hz,); 13C nmr (deuterio-
chloroform): ꢀ 21.0, 44.6, 48.1, 127.10, 128.0, 128.60, 128.70,
128.80, 133.20, 136.80, 138.30, 173.0, 195.20; Anal. Calcd for
C17H15NO2,(265.11): C, 76.98; H, 5.66; N, 5.28. found: C, 76.87;
H, 5.63; N, 5.32.
trans-5-Benzoyl-2-methyl-4-phenyl-2-oxazoline (4a). Yellow
solid, mp 88-90 °C; ir (potassium bromide): 3070, 2991, 1690,
1648, 1422, 1237, 1058, 762, 692 cm-1; 1H nmr (deuteriochloro-
form): ꢀ 2.8 (s, 3H), 5.5 (d, 1H, J = 7.2 Hz), 5.6 (d, 1H, J = 7.2
Hz), 7.2-7.5 (m, 5H), 7.7-7.8 (m, 3H), 8.1 (d, 2H, J = 7.4 Hz);
13C nmr (deuteriochloroform): ꢀ 21.20, 46.60, 48.10, 125.10,
125.20, 128.20, 128.70, 128.78, 128.80, 128.85, 128.88, 172.60,
195.20; Anal. Calcd. for C17H15NO2 ) 265.11(: C, 76.98; H, 5.66;
N, 5.28. found: C, 76.79; H, 5.58; N, 5.25.
trans-5-Benzoyl-2-(3-nitrophenyl)-4-phenyl-2-oxazoline
(4d). Yellow solid, mp 95-98 °C; ir (potassium bromide): 3069,
1
16933, 1656, 1528, 1348, 1255, 1074, 967, 755, 692 cm-1; H
nmr (deuteriochloroform): ꢀ 5.5 (d, 1H, J = 7.1 Hz), 5.7 (d, 1H, J
= 7.1 Hz), 7.4 (dd, 2H, J = 7.4, 7.8 Hz), 7.56-7.63 (m, 4H), 7.70
(d, 1H, J = 7.8 Hz), 7.75 (d, 1H, J = 7.8 Hz), 8.0 (dd, 2H, J =1.3,
8.6 Hz), 8.1 (d, 2H, J = 7.1 Hz), 8.23-8.27 (m, 2H); 13C nmr
(deuteriochloroform): ꢀ 75, 89, 126, 127.7, 128.80, 128.82,
128.83, 128.9, 129.2, 129.5, 133.4, 135.1, 139.2, 149, 175.0,
196.0; Anal. Calcd. for C22H16N2O4 (372.11): C, 70.97; H, 4.30;
N, 7.53. found: C, 71.31; H, 4.26; N, 7.50.
trans-1,2-Di-benzoyl-3-(3-nitrophenyl)aziridine (2e). White
solid, mp 129-130°C; ir (potassium bromide): 3066, 1689, 1585,
1525, 1355, 1180, 721, 682 cm-1; 1H nmr (deuteriochloroform): ꢀ
4.2 (d, 1H, J = 2.3 Hz), 4.4 (d, 1H, J = 2.3 Hz), 7.4 (dd, 2H, J =
6.9, 7.9 Hz), 7.5 (m, 3H), 7.6 (dd, 2H, J = 2.0, 7.9 Hz), 7.8 (d, 1H,
J = 7.7 Hz), 7.9 (dd, 2H, J = 1.3, 8.7 Hz), 8.0 (dd, 2H, J = 1.2, 8.6
Hz), 8.2-8.3 (m, 1H), 8.3 (dd, 1H, J = 1.9, 3.4 Hz); 13C nmr
(deuteriochloroform): ꢀ 47.0, 49.0, 118.1, 122.2, 125.8, 126.2,
128.1, 128.8, 128.9, 129.5, 131.2, 133.1, 134.2, 135.8, 138.2,
148.1, 170.5, 198.1; Anal. Calcd. for C22H16N2O4 (372.11): C,
70.98; H, 4.34; N, 7.52. found: C, 71.2; H, 4.36; N, 7.68.
trans-1,2-Di-benzoyl-3-phenylaziridine (2b). White solid,
mp 86-88°C. ir (potassium bromide): 3060, 1675, 1596, 1452,
1
1328, 1228 cm-1; H nmr (deuteriochloroform): ꢀ 4.12 (d, 1H, J
= 2.1 Hz), 4.37 (d, 1H, J = 2.1 Hz), 7.4-7.8 (m, 11H), 8.00-8.01
(m, 4H); 13C nmr (deuteriochloroform): ꢀ 48.0, 48.97, 126.93,
128.84, 128.86, 128.92, 129.10, 129.23, 129.33, 132.90, 134.11,
136.18, 136.82, 176.12, 192.15; Anal. Calcd. for C22H17NO2
(327.13): C, 80.73; H, 5.20; N, 4.28. found: C, 80.82; H, 5.15;
N, 4.25.
trans-5-Benzoyl-2,4-di-phenyl-2-oxazoline (4b). Yellow
solid, mp 89-90°C; ir (potassium bromide): 2918, 1689, 1649,
trans-5-Benzoyl-4-(3-nitrophenyl)-2-phenyl-2-oxazoline (4e).
Yellow solid, mp 112-114 °C; ir (potassium bromide): 3068,

Nov-Dec 2008
An Efficient Synthesis of 5-Benzoyloxazolines by Regio- and Stereo-controlled
1769
16923, 1652, 1527, 1346, 1240, 1064, 962, 751, 692 cm-1; H
nmr (deuteriochloroform): ꢀ 5.6 (d, 1H, J = 7.1 Hz), 5.8 (d, 1H, J
= 7.1 Hz), 7.5 (dd, 2H, J = 7.5, 7.7 Hz), 7.56-7.63 (m, 4H), 7.72
(d, 1H, J = 7.8 Hz), 7.75 (d, 1H, J = 7.7 Hz), 8.0 (dd, 2H, J =
1.3, 8.5 Hz), 8.1 (d, 2H, J = 7.1 Hz), 8.23-8.27 (m, 2H); 13C nmr
(CDCl3): ꢀ 74.0, 88.1, 128.6, 128.7,128.73, 128.82, 128.8,
128.9, 129.1, 129.5, 133.2, 134.1, 139.2, 148.0, 173.0, 195.0;
Anal. Calcd. for C22H16N2O4 (372.11): C, 70.98; H, 4.34; N,
7.52. found: 71.31; H, 4.26; N, 7.50.
144.0, 148.2, 166.0, 195.0; Anal. Calcd. for C24H18N2O4
)
398.13(: C, 72.30; H, 4.51; N, 7.01. found: C, 72.50; H, 4.47; N,
7.20.
1
trans--5-Benzoyl-4-(3-nitrophenyl)-2-((E)-2-phenylethenyl)
-2-oxazoline (4h). Yellow solid, mp 117-119 °C; ir (potassium
bromide): 3062, 2958, 2931, 1667, 1025, 1529, 1350, 1228, 975,
1
755, 666 cm-1; H nmr (deuteriochloroform): ꢀ 5.6 (d, 1H, J =
6.8 Hz), 5.7 (d, 1H, J = 6.8 Hz), 7.3 (d, 1H, J = 15.9 Hz), 7.4 (m,
2H), 7.5 (m, 5H), 7.56 (dd, 1H, J = 7.2, 7.8 Hz), 7.6 (dd, 1H, J =
7.2, 7.6 Hz), 7.66 (d, 1H, J = 15.9 Hz), 7.7 (d, 1H, J = 7.6 Hz),
trans-2-Benzoyl-1,3-di-(3-nitrobenzoyl)aziridine (2f).
White solid, mp 132-134 °C; ir (potassium bromide): 3089,
7.75 (d, 2H, J = 7.8 Hz), 7.8 (d, 1H, J = 8.2 Hz), 8.3 (s, 1H); 13
C
1
2925, 1701, 1672, 1527, 1348, 1224, 721, 682 cm-1; H nmr
nmr (deuteriochloroform): ꢀ 75.0, 79.0, 120.0, 121.0, 123.0,
126.0, 126.6, 128.6, 128.7, 128.8, 129.5, 133.0, 133.2, 134.0,
135.2, 137.0, 144.0, 148.2, 167.0, 198.0; Anal. Calcd. for
C24H18N2O4 ) 398.13(: C, 72.30, H; 4.51; N, 7.01. found: C,
72.15; H, 4.37; N, 7.25.
(deuteriochloroform): ꢀ 4.2 (d, 1H, J = 2.6 Hz), 4.6 (d, 1H, J =
2.6 Hz), 7.5 (dd, 2H, J = 7.87, 8.01 Hz), 7.6 (m, 3H), 7.89 (d,
2H, J = 7.7 Hz), 7.9 (dd, 1H, J = 8.1, 0.8 Hz), 8.2 (m, 1H), 8.3-
8.4 (m, 3H), 8.8 (dd, 1H, J = 1.8, 1.9 Hz); 13C nmr (deuterio-
chloroform): ꢀ 47.0, 49.0, 118.1, 123.2, 125.8, 126.1,126.9,
128.1, 128.7, 128.9, 129.5, 132.2, 133.1,135.2, 135.9, 137.2,
147.2, 148.1, 172.5, 197.1; Anal. Calcd. for C22H15N3O6 (417.1):
C, 63.33; H, 3.63; N, 10.06. found: C, 63.5; H, 3.51; N, 9.93.
trans-5-Benzoyl-2,4-di-(3-nitrophenyl)-2-oxazoline (4f).
Yellow solid, mp 106-108 °C; ir (potassium bromide): 3071,
2925, 1693, 1662, 1531, 1350, 750, 707, 682 cm-1; 1H nmr
(deuteriochloroform): ꢀ 5.75 (d, 1H, J = 7.2 Hz), 5.8 (d, 1H, J =
7.2 Hz), 7.5-7.7 (m, 3H), 7.7 (m, 3H), 8.0 (dd, 2H, J = 1.35, 8.5
Hz), 8.2 (m, 2H), 8.4 (dd, 2H, J = 2.0, 8.1 Hz), 8.9 (dd, 1H, J =
1.7, 1.8 Hz); 13C nmr (deuteriochloroform): ꢀ 74.2, 83.2, 117.1,
124.1, 125.5, 126.1,126.8, 128.1, 128.6, 128.9, 129.4, 132.4,
133.1, 135.2, 136.9, 137.4,147.2, 149.1, 172.5, 197.1; Anal.
Calcd. for C22H15N3O6 (417.1): C, 63.33; H, 3.63; N, 10.06.
found: C, 63.50; H, 3.72; N, 9.87.
trans-1-(2-Chlorobenzoyl)-2-benzoyl-3-phenylaziridine (2i).
White solid, mp 139-140 °C; ir (potassium bromide): 3060, 2901,
1
1688, 1649, 1595, 1488, 1265, 1070, 760, 707, 695 cm-1; H nmr
(deuteriochloroform): ꢀ 4.1 (d, 1H, J = 2.4 Hz), 4.4 (d, 1H, J = 2.4
Hz), 7.3 (d, 2H, J = 8.1 Hz), 7.4-7.45 (m, 7H), 7.6 (dd, 1H, J = 1.0,
7.4 Hz), 7.9 (d, 2H, J = 8.1), 8.0 (d, 2H, J = 8.7 Hz); 13C nmr
(deuteriochloroform): ꢀ 48.0, 49.2, 126.9, 128.7, 128.9, 129.2,
129.25, 129.35, 129.4, 130.2, 132.6, 134.5, 135.8, 136.5,
139.2,175.3, 191.9; Anal. Calcd. for C22H16ClNO2 (361.09): C,
73.08; H, 4.47; N, 3.87. found: C, 73.10; H, 4.35; N, 3.65.
trans-5-Benzoyl-2-(2-chlorophenyl)-4-phenyl-2-oxazoline
(4i). Yellow solid, mp 125-127 °C,: ir (potassium bromide):
3060, 2900, 1690, 1649, 1595, 1489, 1448, 1250, 1072, 968,
763, 707, 690 cm-1; 1H nmr (deuteriochloroform): ꢀ 5.5 (d, 1H, J
= 6.6 Hz), 5.77 (d, 1H, J = 6.6 Hz), 7.3 (d, 2H, J = 6.9 Hz), 7.35
(d, 1H, J = 6.2 Hz), 7.4 (d, 2H, J = 7.15 Hz), 7.47 (d, 2H, J = 8.5
Hz), 7.5 (dd, 2H, J = 6.7, 7.8 Hz), 7.6 (dd, 1H, J = 7.2, 7.4 Hz),
7.9 (d, 2H, J = 7.2), 8.0 (d, 2H, J = 6.8); 13C nmr (deuterio-
chloroform): ꢀ 74.2, 87.2, 125.8, 127.4, 128.7, 129.2, 29.3,
129.4, 129.5, 130.5, 134.4, 134.6, 138.6, 141.2, 163.4, 194.6;
Anal. Calcd. for C22H16ClNO2 (361.09): C, 73.08; H, 4.47: N,
3.87. found: C,73.12; H, 4.40; N, 3.77.
trans-2-Benzoyl-1-(2-furyl)-3-phenylaziridine (2g). White
solid, mp 119-122 °C; ir (potassium bromide): 3050, 2992,
1
1675, 1576, 1532, 1470, 1760, 756, 692 cm-1; H nmr (deuterio-
chloroform): ꢀ 4.1 (d, 1H, J = 2.2 Hz), 4.2 (d, 1H, J = 2.2 Hz),
7.1 (dd, 1H, J = 3.6, 4.2 Hz), 7.2 (d, 1H, J = 4.2 Hz), 7.3 (m,
5H), 7.5 (m, 3H), 7.52 (d, 1H, J = 3.6 Hz), 7.9 (d, 2H, J = 7.8
Hz); 13C nmr (deuteriochloroform): ꢀ 45.8, 48.8, 111.6,113.5,
127.1, 128.0, 128.3, 128.6, 133.2, 136.5, 136.9 138.3, 146.2,
147.5, 169.1, 194.5; Anal. Calcd. for C20H15NO3 (317.11): C,
75.75; H, 4.77; N, 4.41. found: C, 75.48; H, 4.51; N, 4.60.
trans-5-Benzoyl-2-(2-furyl)-4-phenyl-2-oxazoline (4g).
White solid, mp 111-113 °C; ir (potassium bromide): 5075,
2925, 1675, 1525, 1230, 757, 694 cm-1; 1H nmr (deuteriochloro-
form): ꢀ 5.6 (d, 1H, J = 7.0 Hz), 5.8 (d, 1H, J = 7.0 Hz), 7.15 (d,
1H, J = 4.3 Hz), 7.18 (dd, 1H, J = 3.6, 4.3 Hz), 7.6 (m, 5H), 7.7
(dd, 1H, J = 7.4, 8.1 Hz), 7.8 (d, 1H , J = 3.6 Hz), 8.0 (d, 2H, J =
7.4 Hz), 8.27(d, 2H, J = 8.6 Hz); 13C nmr (deuteriochloroform):
ꢀ 75.8, 85.8, 112.1, 115.5, 127.2, 128.4, 128.6, 128.9, 132.2,
134.5, 136.9 137.3, 147.2, 147.4, 160.1, 196.5; Anal. Calcd. for
C20H15NO3 (317.11): C, 75.75; H, 4.77; N, 4.41. found: C, 75.55;
H, 4.62; N, 4.50.
N-((R)-2-Chloro-1,3-diphenyl-1-oxo-propan-2-yl)acetamide
(3a). White solid, mp 88-91°C; ir (potassium bromide): 3286,
1
3085, 2950, 1685, 1637, 1520, 1355, 757, 696 cm-1; H nmr
(deuteriochloroform): ꢀ 2.1 (s, 3H), 5.4 (d, 1H, J = 7.0 Hz), 6.2
(dd, 1H, J = 7.0, 8.8 Hz), 6.5 (d, 1H, J = 8.8 Hz), 7.8 (m, 3H),
7.5-7.6 (m, 5H), 8.1 (d, 2H, J = 7.2 Hz); 13C nmr (deuterio-
chloroform): ꢀ = 24.1, 128.7, 128.8, 129.2, 129.4, 130.1, 131.6,
132.1 133.2, 136.8, 138.0, 170.0, 195.0; Anal. Calcd. for
C17H16ClNO2 (301.77): C, 67.70; H, 5.30; N, 4.60. found: C,
67.50; H, 5.50; N, 4.71.
Acknowledgments. We are thankful to Research Council of
University of Guilan for the partial support of this work.
trans-2-Benzoyl-1-cinnamoyl-3-(3-nitrophenyl)aziridine
(2h). White solid, mp 138-140 °C; ir (potassium bromide): 3062,
2958, 2931, 1667, 1025,1529, 1350, 1228, 975, 755, 666 cm-1;
1H nmr (deuteriochloroform): ꢀ 4.1 (d, 1H, J = 2.1 Hz), 4.3 (d,
1H, J = 2.1 Hz), 6.5 (d, 1H, J = 15.9 Hz), 7.4 (m, 2H), 7.5 (m,
5H), 7.64 (dd, 1H, J = 7.1, 7.8 Hz), 7.7 (dd, 1H, J = 7.2, 7.7 Hz),
7.8 (d, 1H, J = 15.9 Hz), 7.85 (d, 1H , J = 7.6 Hz), 8.0 (d, 2H, J =
7.6 Hz), 8.2 (d, 1H, J = 8.1 Hz), 8.3 (s, 1H); 13C nmr
(deuteriochloroform): ꢀ 44.0, 48.0, 119.0, 119.3, 123, 126, 12.4,
128.7, 128.8, 128.9, 129.5, 133, 133.2, 134.0, 135.2, 136.4,
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