Synthesis of N-aryl-2-oxazolidinones from cyclic carbonates and aromatic amines catalyzed by bio-catalyst

Article abstract of DOI:10.1007/s11164-017-3222-y

A convenient and effective method of synthesizing 3-aryl-2-oxazolidinones from cyclic carbonates and aryl amines catalyzed by bio-catalyst adenine in the presence of Et₃N under solvent-free conditions is described. The protocol is suitable for the wide scope of substrates, e.g. cyclic carbonates with or without substitutes, and aryl amines with either electron-withdrawing or electron-donating group. The products were obtained in good to excellent yields under the optimal conditions, even in steric hindered cases. The effect of reaction time, temperature, loading of catalyst, and amount of starting materials in the reaction were investigated, and the reaction mechanism is discussed.

Full text of DOI:10.1007/s11164-017-3222-y

Res Chem Intermed
https://doi.org/10.1007/s11164-017-3222-y
Synthesis of N‑aryl‑2‑oxazolidinones from cyclic
carbonates and aromatic amines catalyzed
by bio‑catalyst
Congmin Mei1 · Yibo Zhao1 · Ke Zou1 · Changsheng Cao1 · Guangsheng Pang2 ·
Yanhui Shi1
Received: 25 July 2017 / Accepted: 4 December 2017
© Springer Science+Business Media B.V., part of Springer Nature 2017
Abstract A convenient and efective method of synthesizing 3-aryl-2-oxazolidi-
nones from cyclic carbonates and aryl amines catalyzed by bio-catalyst adenine in
the presence of Et3N under solvent-free conditions is described. The protocol is suit-
able for the wide scope of substrates, e.g. cyclic carbonates with or without substi-
tutes, and aryl amines with either electron-withdrawing or electron-donating group.
The products were obtained in good to excellent yields under the optimal conditions,
even in steric hindered cases. The efect of reaction time, temperature, loading of
catalyst, and amount of starting materials in the reaction were investigated, and the
reaction mechanism is discussed.
Keywords 3-Aryl-2-oxazolidinone · Adenine · Bio-catalyst · Hydrogen bond
donor · Solvent-free
Electronic supplementary material The online version of this article (https://doi.org/10.1007/
s11164-017-3222-y) contains supplementary material, which is available to authorized users.
*
*
Changsheng Cao
chshcao@jsnu.edn.cn
Yanhui Shi
yhshi@jsnu.edu.cn
1
2
School of Chemistry and Material Science and Jiangsu Key Laboratory of Green Synthetic
Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu,
People’s Republic of China
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry,
Jilin University, Changchun 130012, Jilin, People’s Republic of China
1 3

C. Mei et al.
Introduction
As important heterocyclic compounds, 3-aryl-2-oxazolidinones have attracted
signifcant interest over the past few decades. They have exhibited many poten-
tial biological activities and are widely applied in the pharmaceutical industry
[1]. For example, they exhibit a good inhibitory efect on monoamine oxidase A
[2] and potent activities against Gram-positive bacterial pathogens [1, 3], includ-
ing methcillin-resistant Staphylococcus aureus (MRSA) [4, 5], methcillin-resist-
ant Staphylococcus epidermidis (MRSE) and vancomycin-resistant Enterococci
(VRE) [6]. Furthermore, oxazolidinones are important intermediates in preparing
small organic molecules and polymers [7–10]. Chiral oxazolidinones are often
used as chiral synthons or chiral auxiliaries in organic synthesis [11–15].
Not surprising, much efort has been made to synthesize these useful hetero-
cycles. The classical method is by the reaction of phosgene with 2-alkylamine
[16]; however, use of toxic materials is limitation of this method. Alternatively,
oxazolidinones can be prepared by the reactions of epoxides with isocyanate
[17–19], oxazolidin-2-ones with aryl halides [20–24], amino alcohol carbamates
with aryl iodides [25], 2-(arylamino) alcohols with diethyl carbonate [26, 27],
or carbamothioates with propargylic carbamates [28]. Recently, more research
has focused on using carbon dioxide in the synthesis of oxazolidinones [29–36].
However, these methods encounter many problems, such as unavailable prefunc-
tionalized substrates [17–19, 26, 27, 36] and the complex catalysts, which require
tedious steps to obtain [17–19, 24]. Besides these, high reaction temperature
[20, 23–25, 36], long reaction time [21, 24, 25, 33], high pressure [29–34] and
purity of carbon dioxide [30] are usually required. There is a very convenient
way to prepare oxazolidinones, which is from readily available cyclic carbonates
and aromatic amines [37–40]. According to the existing literature, there are two
types of catalysts used for the synthetic method. The frst type is an organic base
as catalyst, such as DABCO [37] (1,4-Diazabicyclo[2.2.2]octane; triethylenedi-
amine) or DBU [38] (1,8-Diazabicyclo[5.4.0]undec-7-ene). However, the base
has to be used in a large quantity (1–2 equivalent), and the hindrance efect is
very signifcant for anilines bearing ortho-substituents groups, leading very low
yield or even no yield of products. Furthermore, the substituted cyclic carbon-
ates have not been tested in these protocols. Another type of catalyst used in this
reaction is imidazole-based ionic liquid [39, 40]. However, these catalysts are still
not efective for steric hindered anilines. Therefore, it is necessary to develop an
environment-friendly and efcient catalyst to catalyze substituted cyclic carbon-
ates with steric hindered aryl amines.
In many catalytic processes, organocatalysts have usually worked as hydrogen
bond donors (HBDs) to active the substrates [41]. It is very interesting to use
naturally available compounds as HBDs in catalytic processes, as they are readily
available, inexpensive and have low toxicity. Unfortunately, this type of applica-
tion is quite rare [42]. As a former member of vitamin B, adenine is inexpensive
and nontoxic (Scheme 1); however, there are very limited reports using adenine
as an organocatalyst [43]. We envisage that it might be used as HBD through NH2
1 3

Synthesis of N‑aryl‑2‑oxazolidinones from cyclic carbonates…
Scheme 1 Structure of adenine
group. Herein, we report that the use of adenine as the efcient hydrogen bond
donor to synthesize oxazolidiones from aromatic amines and cyclic carbonates
under solvent-free conditions in good yields.
Results and discussion
Efect of diferent bases
Firstly, diferent bases were explored in the reaction of aniline with 1,3-dioxolan-
2-one catalyzed by adenine, and the results are summarized in Table 1. In all tested
inorganic bases, sodium tert-butoxide (t-BuONa) gave the highest of yield of 3-phe-
nyl-2-oxazolidinone (79%), which is comparable to KHCO3 (73%) (Table 1, entries
Table 1 Screening of various bases for the synthesis of 3-phenyl-2-oxazolidinone
Entrya
Adenine (mol%)
Base
Yield (%)b
1
2
3
4
5
6
7
8
10
10
10
10
10
10
10
10
10
10
10
–
KOAc
NH4OAc
K3PO4
KHCO3
NaHSO4
Cs2CO3
t-BuONa
t-BuOK
Et3N
43
24
52
73
0
44
79
35
96
56
0
9
10
11
12
DBU
–
Et3N
30
aReaction conditions adenine (0–0.1 mmol), base (0–0.5 mmol), aniline (1 mmol, 91 μL), 1,3-dioxolan-
2-one (5 mmol, 0.44 g), 110 °C, 24 h
bGC yield
1 3

C. Mei et al.
4 and 7). The other bases, such as KOAc, K3PO4, NH4OAc, Cs2CO3 gave less than
or about 50% yield of the product, whereas no product was observed with NaHSO4
(Table 1, entry 5). However, an excellent yield of product (96%) was obtained with
the organic base triethylamine (Et3N) (Table 1, entry 9), whereas another organic
base DBU showed moderate catalytic activity (56%). Two control reactions were
performed, showing that the reaction would not be catalyzed by adenine alone
(Table 1, entry 11). In addition, only 30% of the product was observed with only
Et3N used.
Efect of reaction conditions
The efect of amount of Et3N, adenine and 1,3-dioxolan-2-one on the reaction was
investigated in the same reaction, and the results are provided in Fig. 1. The results
(Fig. 1a) show that the yield of product dramatically increased when the amount
of Et3N increased from 20 to 50 mol%, whereas it decreased with the further
increase of Et3N from 50 to 80 mol%. Therefore, the highest yield was achieved
when 50 mol% of Et3N was used. As shown in Fig. 1b, the highest yield of the
product was observed with 5 mol% of adenine, whereas more or less of the adenine
loading would lead to less formation of 3-phenyl-2-oxazolidinone. In addition, the
equivalent of 1,3-dioxolan-2-one used also has a big efect on the reaction (Fig. 1c).
The yield of the product increased signifcantly when the equivalent of 1,3-dioxolan-
2-one was increased from 3 to 5 eq., then no obvious change was observed with
more than 5 eq. of 1,3-dioxolan-2-one.
Next, the infuence of reaction time and temperature was investigated (Fig. 2). As
shown in Fig. 2a, the yield increased with extension of the reaction time from 10 to
18 h. No signifcant increase of yield happened after 18 h. The efect of temperature
on the reaction was investigated from 60 to 120 °C. The results showed that the
yield of 3-phenyl-2-oxazolidinone initially increased with elevation of the reaction
temperature, then no change of the yield was observed when the temperature was
higher than 110 °C (Fig. 2b).
100
90
80
70
60
50
40
30
20
100
90
80
70
60
50
40
100
90
80
70
60
50
c
b
a
0
10
20
30
40
50
3
4
5
6
7
8
9
20
30
40
50
60
70
80
Loading of adenine (mol%)
Loading of Et N (mol%)
1,3-dioxolan-2-one (eq.)
3
Fig. 1 Efect of loading of Et3N (mol%) (a), adenine (b) and 1,3-dioxolan-2-one (c) on the yield
of 3-phenyl-2-oxazolidinone. Reaction conditions: aniline (1 mmol, 91μL), 110 °C, 24 h. a adenine
(0.1 mmol, 13.4 mg), Et3N (0.2–0.8 mmol), 1,3-dioxolan-2-one (6 mmol, 0.528 g), b adenine (0.001–
0.5 mmol), Et3N (0.5 mmol, 69 μL), 1,3-dioxolan-2-one (6 mmol, 0.528 g), c adenine (0.05 mmol,
6.7 mg), Et3N (0.5 mmol, 69 μL), 1,3-dioxolan-2-one (3-8 mmol). GC yield. Using dodecane as internal
standard and the average of two runs
1 3

Synthesis of N‑aryl‑2‑oxazolidinones from cyclic carbonates…
100
80
60
40
20
0
100
90
80
70
60
50
b
a
60
70
80
90
100
110
120
10
12
14
16
18
20
22
Temp (oC)
Time (h)
Fig. 2 Efect of reaction time (a), temperature (b) on the yield of 3-phenyl-2-oxazolidinone. Reaction
conditions: adenine (0.05 mmol, 6.7 mg), Et3N (0.5 mmol, 69 μL), aniline (1 mmol, 91 μL), 1,3-diox-
olan-2-one (6 mmol, 0.528 g). a 110 °C, 10–22 h, b 60–120 °C, 18 h. GC yield. Using dodecane as inter-
nal standard and the average of two runs
In order to further test the general applicability of this protocol, a variety of
aryl amines were selected and tested in the synthesis of 3-aryl-2-oxazolidinones.
All reactions were carried out with 5 mol% of adenine and 50 mol% of Et3N at
110 °C for 18 h. Initially, various aromatic amines were employed to react with
Table 2 Reaction of cyclic carbonates and aromatic amines catalyzed by adenine
Reaction conditions adenine (0.05 mmol, 6.7 mg), Et3N (0.5 mmol, 69 μL), aryl amine (1 mmol), cyclic
carbonate (6 mmol), 18 h
a29a–33a, 120 °C
1 3

C. Mei et al.
1,3-dioxolan-2-one (Table 2, compounds 1a–28a). As shown in Table 2, anilines
with either electron withdrawing groups (such as CN, F, CF3, Cl, NO2, etc.) or
electron-donating groups (such as Me, Et, n-Bu, OMe) were converted smoothly
to the corresponding 3-aryl-2-oxazolidinones in good to excellent yields (74–97%)
(Table 2, compounds 1a–23a). Notably, the steric efect on reaction is insignifcant,
for example, all anilines with substituents in ortho, meta or para position could be
converted to the product in good to excellent yields (74–97%) (Table 2, 5a–23a).
Furthermore, the reaction tolerates rather well the presence of severe steric hin-
drance near the reaction site (Table 2, 24a–26a). Naphthalenyl amines were con-
verted to the 3-naphthalenyl-2-oxazolidinones in good yields as well, such as 27a
(97%) and 28a (95%). Then, mono-substituted cyclic carbonates were investigated
in the reaction (Table 2, 29a–33a). The reaction of 4-methyl-1,3-dioxolan-2-one and
4-phenyl-1,3-dioxolan-2-one with aniline proceeded very well, which aforded the
corresponding products, 29a–32a in yields ranging from 69 to 95% with good regi-
oselectivity. This system is also suitable for the reactions of mono-substituted cyclic
carbonates with naphthalenyl amines, afording 33a in the yield of 85%. It is worthy
of note that the yields decreased with increasing the size of substituent R1 on cyclic
carbonates in the following order: 1,3-dioxolan-2-one > 4-methyl-1,3-dioxolan-
2-one > 4-phenyl-1,3-dioxolan-2-one when the same amine was used (7a, 31a and
32a), indicating that steric hindrance of cyclic carbonates infuences the reactivity,
to some extent.
Compared to the other catalysts described in the literature [37–40], this catalytic
system is more efective in the following aspects: less catalytic loading, higher yield
and general applicability in wide scope of substrates. For example, for the organic
base catalysts [37, 38], the catalyst has been used over stoichiometric amount; the
yield of the product is generally lower; only 13 examples are provide and substituted
cyclic carbonate is not tested. For ionic liquids catalysts [39, 40], the yield of the
product is generally lower; only 19 examples are provided, and the result of the reac-
tion with steric hinder aniline is not available.
Mechanistic studies
To understand the reaction mechanism and the role of adenine and Et3N in the
reaction, an LC–MS sample was prepared from the reaction mixture of 1,3-diox-
olan-2-one with aniline when the reaction was carried out 9 h. From the LC–MS
spectra, a substance with molecular weight of 223.1 was found, which is consistent
with the total molecular weight of 1,3-dioxolan-2-one and adenine. In addition, a
large amount of the substance with molecular weight of 181.2 was detected, which
matches the molecular weight of 2-hydroxyethyl phenylcarbamate, the open ring
product of 1,3-dioxolan-2-one by aniline.
According to these results, we propose the following mechanism for the reaction
(Scheme 2). Firstly, 1,3-dioxolan-2-one is activated by adenine through an inter-
action of hydrogen bonding to form intermediate i (Mol. Wt. = 223.1). A nucleo-
philic attack of activated 1,3-dioxolan-2-one by aniline aford a ring opening prod-
uct, 2-hydroxyethyl phenylcarbamate (ii) (Mol. Wt. = 181.2) and regenerate free
1 3

Synthesis of N‑aryl‑2‑oxazolidinones from cyclic carbonates…
Scheme 2 The proposed reaction mechanism
adenine. Deprotonation of ii by trimethylamine gives an amide anion, following
nucleophilic substitution to generate the cyclization product.
Conclusions
In summary, being a hydrogen bond donor, the inexpensive, non-toxic, environmen-
tally friendly and readily available adenine was discovered to be an efcient bio-
catalyst for the preparation of 3-aryl-2-oxzaolidiones from unsubstituted and mono-
substituted cyclic carbonates with aryl amine under solvent-free conditions. This
reaction is applicable to an extensive range of substituted aryl amines, and even the
steric hindered di-substituted aryl amine. Good to excellent yields of 3-aryl-2-ox-
zaolidiones were aforded using aryl amines with either electron-withdrawing or
electron-donating group.
1 3

C. Mei et al.
Experimental
All substrates and reagents are commercially available and were used as received.
Aryl amines (> 96%) and adenine (> 98%) were purchased from Energy Chemi-
cal. The deuterated solvent, CCl3D was obtained from Cambridge Isotope Labora-
tories, Inc. All other chemicals were analytical grade and were supplied by Sinop-
1
harm Chemical Reagent Beijing Co., Ltd. H and 13C NMR spectra were recorded
on Bruker AV400 spectrometer. Chemical shift values are expressed in ppm relative
to solvent residue. GC–MS was performed on an Agilent 6890-5973 N system with
electron ionization (EI) mass spectrometry. IR spectra were recorded on KBr pellets
on a FTIR-Tensor 27 spectrometer. HRMS was recorded on a Fisher LTQ-Orbitrap
XL combined-type mass spectrometry.
General procedure for the synthesis of oxazolidinones
An 8 mL vial was charged with adenine (0.05 mmol, 6.7 mg), Et3N (0.5 mmol,
69 μL), aryl amine (1 mmol) and cyclic carbonate (6 mmol). The mixture was
heated at 110 °C for 18 h, after which time 5 mL of water was added. The organic
layer was extracted with dichloromethane (3 × 5 mL). The combined organic phase
was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The
residue was purifed by fash column chromatography on silica gel (petroleum ether/
ethyl acetate = 5:1 as eluent).
3‑phenyloxazolidin‑2‑one (1a) [37] White solid; mp 120.0–122.5 °C; IR (KBr,
ν, cm−1): 1740 (C=O), 1410 (C–H), 1318 (C–N), 1221 (C–N), 1128 (C–N), 1050
1
(C–C), 753 (C–H), 689 (C–H); H NMR (400 MHz, CDCl3), (δ, ppm): 7.54 (d,
J = 8.4 Hz, 2H, ArH), 7.38 (t, J = 7.6 Hz, 2H, ArH), 7.14 (t, J = 7.6 Hz, 1H,
ArH), 4.48 (t, J = 7.6 Hz, 2H, OCH2), 4.06 (t, J = 8.0 Hz, 2H, NCH2); 13C NMR
(100 MHz, CDCl3), (δ, ppm): 155.4 (C=O), 138.4 (ArC), 129.2 (ArC), 124.2 (ArC),
118.4 (ArC), 61.4 (OCH2), 45.3 (NCH2).
3‑(4‑ethylphenyl)oxazolidin‑2‑one (2a) [47] White solid; mp 63.0–65.0 °C;
IR (KBr, ν, cm−1): 1736 (C=O), 1614 (C=C), 1517 (C=C), 1426 (C=C), 1314
1
(C–N), 1222 (C–N), 1131 (C–N), 1052 (C–O), 1003 (C–O), 841 (C–H); H NMR
(400 MHz, CDCl3), (δ, ppm): 7.44 (d, J = 8.4 Hz, 2H, ArH), 7.20 (d, J = 8.4 Hz,
2H, ArH), 4.46 (t, J = 7.6 Hz, 2H, OCH2), 4.03 (t, J = 8.4 Hz, 2H, NCH2), 2.63 (dd,
J = 19.2 Hz, J = 11.6 Hz, 2H, ArCH2), 1.22 (t, J = 7.6 Hz, 3H, ArCH2CH3); 13C
NMR (100 MHz, CDCl3), (δ, ppm): 155.5 (C = O), 140.3 (ArC), 136.0 (ArC), 128.5
(ArC), 118.6 (ArC), 61.4 (OCH2), 45.5 (NCH2), 28.3 (ArCH2), 15.8 (ArCH2CH3).
3‑(4‑butylphenyl)oxazolidin‑2‑one (3a) Yellow solid; mp 69.5–73.5 °C; IR (KBr,
ν, cm−1): 1732 (C=O), 1617 (C=C), 1519 (C=C), 1484 (C=C), 1432 (C=C), 1319
1
(C–N), 1232 (C–N), 1137 (C–N), 1046 (C–O), 1004 (C–O), 812 (C–H); H NMR
(400 MHz, CDCl3), (δ, ppm): 7.43 (d, J = 8.4 Hz, 2H, ArH), 7.18 (d, J = 8.8 Hz,
1 3

Synthesis of N‑aryl‑2‑oxazolidinones from cyclic carbonates…
2H, ArH), 4.46 (d, J = 8.0 Hz, 2H, OCH2), 4.03 (d, J = 8.4 Hz, 2H, NCH2), 2.58
(t, J = 3.6 Hz, 2H, 1–Bu–CH2), 1.61–1.54 (m, 2H, 2–Bu–CH2), 1.39–1.29 (m, 2H,
3–Bu–CH2), 0.92 (t, J = 6.8 Hz, 3H, 4–Bu–CH3); 13C NMR (100 MHz, CDCl3),
(δ, ppm): 155.5 (C = O), 139.0 (ArC), 136.0 (ArC), 129.1 (ArC), 118.5 (ArC), 61.4
(OCH2), 45.5 (NCH2), 35.0 (1–Bu–CH2), 33.8 (2–Bu–CH2), 22.4(3–Bu–CH2), 14.1
(4–Bu–CH3); HRMS m/z calculated for C13H17NO2Na [M + Na]+: 242.1157; found:
242.1136.
3‑(4‑cyano)oxazolidin‑2‑one (4a) [20] Yellow solid; mp 142.0–144.0 °C; IR (KBr,
ν, cm−1): 1743 (C=O), 1607 (C=C), 1508 (C=C), 1405 (C=C), 1327 (C–N), 1216
1
(C–N), 1135 (C–N), 1052 (C–O), 1004 (C–O), 823 (C–H); H NMR (400 MHz,
CDCl3), (δ, ppm): 7.69–7.63 (m, 4H, ArH), 4.53 (t, J = 8.0 Hz, 2H, OCH2), 4.09
(t, J = 8.0 Hz, 2H, NCH2); 13C NMR (100 MHz, CDCl3), (δ, ppm): 154.7 (C=O),
142.2 (ArC), 133.3 (ArC), 118.8 (ArC), 117.9 (CN), 107.0 (ArC), 61.5 (OCH2),
44.8 (NCH2).
3‑(o‑tolyl)oxazolidin‑2‑one (5a) [37] White oil; IR (KBr, ν, cm−1): 1748 (C=O),
1626 (C=C), 1496 (C=C), 1405 (C=C), 1276 (C–N), 1220 (C–N), 1139 (C–N),
1035 (C–O), 982 (C–O), 750 (C–H); 1H NMR (400 MHz, CDCl3), (δ, ppm): 7.25–
7.19 (m, 4H, ArH), 4.44 (t, J = 7.6 Hz, 2H, OCH2), 3.87 (t, J = 8.0 Hz, 2H, NCH2),
2.28 (s, 3H, ArCH3); 13C NMR (100 MHz, CDCl3), (δ, ppm): 156.7 (C = O), 136.0
(ArC), 135.8 (ArC), 131.2 (ArC), 128.0 (ArC), 126.9 (ArC), 126.3 (ArC), 62.3
(OCH2), 47.7 (NCH2), 17.7 (CH3).
3‑(m‑tolyl)oxazolidin‑2‑one (6a) [20] Yellow solid; mp 84.0–86.0 °C; IR (KBr,
ν, cm−1): 2925 (C–H), 1736 (C=O), 1608 (C=C), 1497 (C=C), 1401 (C=C), 1324
(C–N), 1229 (C–N), 1120 (C–N), 1050 (C–O), 995 (C–O), 781 (C–H), 753 (C–H);
1H NMR (400 MHz, CDCl3), (δ, ppm): 7.39 (s, 1H, ArH), 7.32–7.26 (m, 2H, ArH),
6.66 (d, J = 7.6 Hz, 1H, ArH), 4.48 (t, J = 7.6 Hz, 2H, OCH2), 4.04 (t, J = 7.6 Hz,
2H, NCH2), 2.37 (s, 3H, ArCH3); 13C NMR (100 MHz, CDCl3), (δ, ppm): 155.5
(C=O), 139.2 (ArC), 138.4 (ArC), 129.1 (ArC), 125.1 (ArC), 118.2 (ArC), 115.6
(ArC), 61.5 (OCH2), 45.5 (NCH2), 21.8 (CH3).
3‑(p‑tolyl)oxazolidin‑2‑one (7a) [48] Yellow solid; mp 90.0–91.0 °C; IR (KBr,
ν, cm−1): 1738 (C=O), 1519 (C=C), 1474 (C=C), 1418 (C=C), 1321 (C–N), 1223
1
(C–N), 1130 (C–N), 1047 (C–O), 996 (C–O), 820 (C–H); H NMR (400 MHz,
CDCl3), (δ, ppm): 7.41 (d, J = 8.4 Hz, 2H, ArH), 7.18 (d, J = 8.0 Hz, 2H, ArH),
4.46 (t, J = 7.6 Hz, 2H, OCH2), 4.03 (t, J = 8.4 Hz, 2H, NCH2), 2.33 (s, 3H,
ArCH3); 13C NMR (100 MHz, CDCl3), (δ, ppm): 155.6 (C=O), 135.9 (ArC), 134.0
(ArC), 129.8 (ArC), 118.6 (ArC), 61.5 (OCH2), 45.6 (NCH2), 21.0 (CH3).
3‑(3‑chlorophenyl)oxazolidin‑2‑one (8a) [48] Yellow solid; mp 53.0–54.0 °C; IR
(KBr, ν, cm−1): 1739 (C=O), 1599 (C=C), 1491 (C=C), 1407 (C=C), 1333 (C–N),
1227 (C–N), 1134 (C–N), 1049 (C–O), 967 (C–O), 776 (C–H), 712 (C–H); 1H NMR
(400 MHz, CDCl3), (δ, ppm): 7.58 (s, 1H, ArH), 7.45 (d, J = 8.2 Hz, 1H, ArH), 7.29
1 3

C. Mei et al.
(t, J = 8.0 Hz, 1H, ArH). 7.11 (d, J = 7.6 Hz, 1H, ArH), 4.50 (t, J = 7.6 Hz, 2H,
OCH2), 4.04 (t, J = 8.4 Hz, 2H, NCH2); 13C NMR (100 MHz, CDCl3), (δ, ppm):
155.1 (C=O), 139.6 (ArC), 135.1 (ArC), 130.3 (ArC), 124.3 (ArC), 118.4 (ArC),
116.3 (ArC), 61.5 (OCH2), 45.3 (NCH2).
3‑(4‑chlorophenyl)oxazolidin‑2‑one (9a) [48] Yellow solid; mp 118.5–119.0 °C;
IR (KBr, ν, cm−1): 2924 (C–H), 1735 (C=O), 1599 (C=C), 1500 (C=C), 1424
(C=C), 1406 (C=C), 1322 (C–N), 1218 (C–N), 1128 (C–N), 1049 (C–O), 1002
1
(C–O), 813 (C–H); H NMR (400 MHz, CDCl3), (δ, ppm): 7.50 (d, J = 8.8 Hz,
2H, ArH), 7.34 (d, J = 8.8 Hz, 2H, ArH), 4.48 (t, J = 7.6 Hz, 2H, OCH2), 4.05
(t, J = 8.4 Hz, 2H, NCH2); 13C NMR (100 MHz, CDCl3), (δ, ppm): 155.3 (C=O),
137.1 (ArC), 129.6 (ArC), 129.3 (ArC), 118.6 (ArC), 61.5 (OCH2), 45.4 (NCH2).
3‑(4‑iodophenyl)oxazolidin‑2‑one (10a) [48] White solid; mp 162.0–163.5 °C;
IR (KBr, ν, cm−1): 1728 (C=O), 1584 (C=C), 1484 (C=C), 1416 (C=C), 1308
(C–N), 1224 (C–N), 1130 (C–N), 1043 (CO–O), 998 (C–O), 826 (C–H); 1H
NMR (400 MHz, CDCl3), (δ, ppm): 7.67–7.63 (m, 2H, ArH), 7.33–7.29 (m, 2H,
ArH), 4.47 (t, J = 7.6 Hz, 2H, OCH2), 4.01 (t, J = 8.8 Hz, 2H, NCH2); 13C NMR
(100 MHz, CDCl3), (δ, ppm): 155.1 (C=O), 138.2 (ArC), 138.0 (ArC), 120.0 (ArC),
87.5 (ArC), 61.4 (OCH2), 45.0 (NCH2).
3‑(4‑(trifuoromethyl)phenyl)oxazolidin‑2‑one (11a) [48] White solid; mp 93.5–
95.5 °C; IR (KBr, ν, cm−1): 1733 (C=O), 1617 (C=C), 1523 (C=C), 1477 (C=C),
1295 (C–N), 1226 (C–N), 1160 (C–N), 1050 (C–O), 997 (C–O), 845 (C–H);
1H NMR (400 MHz, CDCl3), (δ, ppm): 7.65 (dd, J = 24.4 Hz, J = 13.2 Hz, 4H,
ArH), 4.53 (t, J = 7.6 Hz, 2H, OCH2), 4.09 (t, J = 8.8 Hz, 2H, NCH2); 13C NMR
(100 MHz, CDCl3), (δ, ppm): 155.0 (C=O), 141.3 (ArC), 126.4 (q, J = 2.6 Hz,
ArC), 126.3 (d, J = 32.8 Hz, ArC), 124.2 (d, J = 270.0 Hz, ArC), 117.8 (ArC), 61.5
(OCH2), 45.0 (NCH2).
3‑(3‑fuorophenyl)oxazolidin‑2‑one (12a) [44] White solid; mp 87.0–88.0 °C; IR
(KBr, ν, cm−1): 1743 (C=O), 1619 (C=C), 1585 (C=C), 1498 (C=C), 1407 (C=C),
1330 (C–N), 1233 (C–N), 1122 (C–N), 1049 (C–O), 984 (C–O), 791 (C–H), 712
1
(C–H); H NMR (400 MHz, CDCl3), (δ, ppm): 7.45–7.41 (m, 1H, ArH), 7.31 (d,
J = 8.0 Hz, 2H, ArH), 6.85–6.80 (m, 1H, ArH), 4.48 (t, J = 7.6 Hz, 2H, OCH2),
4.04 (t, J = 8.4 Hz, 2H, NCH2); 13C NMR (100 MHz, CDCl3), (δ, ppm): 161.9 (d,
J = 250.0 Hz, Ar–F, ArC), 155.0 (C=O), 139.9 (d, J = 11.0 Hz, ArC), 130.3 (d,
J = 9.0 Hz, ArC), 113.3 (d, J = 3.0 Hz, ArC), 110.9 (d, J = 21.0 Hz, ArC), 105.7 (d,
J = 27.0 Hz, ArC), 61.4 (OCH2), 45.2 (NCH2).
3‑(4‑fuorophenyl)oxazolidin‑2‑one (13a) [48] White solid; mp 71.0–72.0 °C; IR
(KBr, ν, cm−1): 1748 (C=O), 1636 (C=C), 1512 (C=C), 1406 (C=C), 1317 (C–N),
1220 (C–N), 1127 (C–N), 1042 (C–O), 913 (C–O), 832 (C–H); 1H NMR (400 MHz,
CDCl3), (δ, ppm): 7.53–7.48 (m, 2H, ArH), 7.11–7.04 (m, 2H, ArH), 4.49 (t,
J = 7.6 Hz, 2H, OCH2), 4.05 (t, J = 8.0 Hz, 2H, NCH2); 13C NMR (100 MHz,
1 3

Synthesis of N‑aryl‑2‑oxazolidinones from cyclic carbonates…
CDCl3), (δ, ppm): 160.7 (d, J = 250.0 Hz, Ar–F, ArC), 155.5 (C=O), 134.5 (d,
J = 2.0 Hz, ArC), 120.2 (d, J = 8.0 Hz, ArC), 116.2 (d, J = 23.0 Hz, ArC), 61.4
(OCH2), 45.6 (NCH2).
3‑(3‑bromophenyl)oxazolidin‑2‑one (14a) [49] White solid; mp 86.0–87.0 °C; IR
(KBr, ν, cm−1): 1743 (C=O), 1593 (C=C), 1497 (C=C), 1398 (C=C), 1313 (C–N),
1
1215 (C–N), 1127 (C–N), 1044 (C–O), 992 (C–O), 749 (C–H), 700 (C–H); H
NMR (400 MHz, CDCl3), (δ, ppm): 7.72–7.71 (m, 1H, ArH), 7.54–7.51 (m, 1H,
ArH), 7.28–7.22 (m, 2H, ArH), 4.50 (t, J = 7.6 Hz, 2H, OCH2), 4.04 (t, J = 8.4 Hz,
2H, NCH2); 13C NMR (100 MHz, CDCl3), (δ, ppm): 155.0 (C=O), 139.7 (ArC),
130.5 (ArC), 127.2 (ArC), 123.0 (ArC), 121.1 (ArC), 116.7 (ArC), 61.4 (OCH2),
45.2 (NCH2).
3‑(4‑bromophenyl)oxazolidin‑2‑one (15a) [48] White solid; mp 132.0–133.0 °C;
IR (KBr, ν, cm−1): 1740 (C=O), 1590 (C=C), 1490 (C=C), 1400 (C = C), 1316
1
(C–N), 1219 (C–N), 1129 (C–N), 1054 (C–O), 996 (C–O), 820 (C–H); H NMR
(400 MHz, CDCl3), (δ, ppm): 7.50–7.43 (m, 4H, ArH), 4.50 (t, J = 7.6 Hz, 2H,
OCH2), 4.04 (t, J = 8.0 Hz, 2H, NCH2); 13C NMR (100 MHz, CDCl3), (δ, ppm):
155.1 (C=O), 137.5 (ArC), 132.1 (ArC), 119.8 (ArC), 117.0 (ArC), 61.4 (OCH2),
45.2 (NCH2).
3‑(3,4‑dichlorophenyl)oxazolidin‑2‑one (16a) [48] White solid; mp 119.5–
122.0 °C; IR (KBr, ν, cm−1): 2926 (C–H), 1749 (C=O), 1597 (C=C), 1482 (C=C),
1317 (C–N), 1218 (C–N), 1145 (C–N), 1049 (C–O), 1004 (C–O), 843 (C–H), 751
(C–H); 1H NMR (400 MHz, CDCl3), (δ, ppm): 7.67 (d, J = 2.0 Hz, 1H, ArH), 7.47–
7.41 (m, 2H, ArH), 4.51 (t, J = 7.6 Hz, 2H, OCH2), 4.04 (t, J = 8.4 Hz, 2H, NCH2);
13C NMR (100 MHz, CDCl3), (δ, ppm): 154.9 (C=O), 137.9 (ArC), 133.2 (ArC),
130.7 (ArC), 127.6 (ArC), 118.8 (ArC), 117.4 (ArC), 61.4 (OCH2), 45.1 (NCH2).
3‑(3‑chloro‑4‑fuorophenyl)oxazolidin‑2‑one (17a) White solid; mp 100.0–
102.0 °C; IR (KBr, ν, cm−1): 1740 (C=O), 1636 (C=C), 1505 (C=C), 1406 (C=C),
1326 (C–N), 1223 (C–N), 1131 (C–N), 1049 (C–O), 1003 (C–O), 813 (C–H), 753
1
(C–H), 706 (C–H); H NMR (400 MHz, CDCl3), (δ, ppm): 7.64 (dd, J = 6.4 Hz,
J = 2.8 Hz, 1H, ArH), 7.45–7.41 (m, 1H, ArH), 7.15 (t, J = 8.8 Hz, 2H, ArH), 4.50
(t, J = 7.6 Hz, 2H, OCH2), 4.04 (t, J = 8.0 Hz, 2H, NCH2); 13C NMR (100 MHz,
CDCl3), (δ, ppm): 156.0 (d, J = 245 Hz, Ar–F, ArC), 155.1 (C=O), 135.2 (ArC),
121.6 (d, J = 17.6 Hz, Ar–F, ArC), 120.5 (ArC), 117.9 (d, J = 6.8 Hz, ArC), 116.9
(d, J = 22.0 Hz, ArC), 61.4 (OCH2), 45.4 (NCH2); HRMS (ESI) m/z calculated for
C9H8ClFNO2Na [M + Na]+: 238.0047; found: 238.0020.
3‑(3‑chloro‑4‑methylphenyl)oxazolidin‑2‑one (18a) [48] White solid; mp 86.0–
88.0 °C; IR (KBr, ν, cm−1): 1755 (C=O), 1616 (C=C), 1504 (C=C), 1403 (C=C),
1320 (C–N), 1218 (C–N), 1129 (C–N), 1072 (C–O), 913 (C–O), 744 (C–H);
1H NMR (400 MHz, CDCl3), (δ, ppm): 7.54 (d, J = 2.4 Hz, 1H, ArH), 7.39
(dd, J = 4.4 Hz, J = 2.4 Hz, 1H, ArH), 7.22 (d, J = 8.0 Hz, 1H, ArH), 4.49 (t,
1 3

C. Mei et al.
J = 7.6 Hz, 2H, OCH2), 4.03 (t, J = 8.0 Hz, 2H, NCH2), 2.34 (s, 3H, ArCH3);
13C NMR (100 MHz, CDCl3), (δ, ppm): 155.2 (C=O), 137.2 (ArC), 134.8 (ArC),
131.8 (ArC), 131.3 (ArC), 118.8 (ArC), 116.6 (ArC), 61.4 (OCH2), 45.3 (NCH2),
19.5 (CH3).
3‑(3‑nitrophenyl)oxazolidin‑2‑one (19a) [44] Yellow solid; mp 110.0–112.0 °C;
IR (KBr, ν, cm−1): 1741 (C=O), 1618 (C=C), 1527 (C=C), 1409 (C=C), 1346
(C–N), 1221 (C–N), 1140 (C–N), 1091 (C–O), 1055 (C–O), 757 (C–H), 700 (C–H);
1H NMR (400 MHz, CDCl3), (δ, ppm): 8.25 (s, 1H, ArH), 8.10 (d, J = 8.4 Hz,
1H, ArH), 7.98 (dd, J = 12.0 Hz, J = 2.4 Hz, 1H, ArH), 7.55 (t, J = 8.4 Hz, 1H,
ArH), 4.46 (t, J = 7.6 Hz, 2H, OCH2), 4.15 (t, J = 8.4 Hz, 2H, NCH2); 13C NMR
(100 MHz, CDCl3), (δ, ppm): 155.0 (C=O), 148.7 (ArC), 139.6 (ArC), 130.1 (ArC),
123.9 (ArC), 118.6 (ArC), 112.4 (ArC), 61.6 (OCH2), 45.1 (NCH2).
3‑(4‑nitrophenyl)oxazolidin‑2‑one (20a) [45] Yellow solid; mp 154.0–155.0 °C;
IR (KBr, ν, cm−1): 1748 (C=O), 1596 (C=C), 1515 (C=C), 1400 (C=C), 1321
1
(C–N), 1260 (C–N), 1110 (C–N), 1052 (C–O), 999 (C–O), 824 (C–H); H NMR
(400 MHz, CDCl3), (δ, ppm): 8.25 (d, J = 9.6 Hz, 2H, ArH), 7.73 (d, J = 9.6 Hz,
2H, ArH), 4.56 (d, J = 7.6 Hz, 2H, OCH2), 4.14 (d, J = 8.4 Hz, 2H, NCH2); 13C
NMR (100 MHz, CDCl3), (δ, ppm): 154.7 (C=O), 143.9 (ArC), 143.4 (ArC), 125.1
(ArC), 117.5 (ArC), 61.5 (OCH2), 45.0 (NCH2).
3‑(2‑methoxyphenyl)oxazolidin‑2‑one (21a) [48] Yellow solid; mp 62.0–63.0 °C;
IR (KBr, ν, cm−1): 1750 (C=O), 1598 (C=C), 1507 (C=C), 1464 (C=C), 1411
(C=C), 1298 (C–N), 1246 (C–N), 1129 (C–N), 1037 (C–O), 985 (C–O), 752 (C–H);
1H NMR (400 MHz, CDCl3), (δ, ppm): 7.36 (dd, J = 7.6 Hz, J = 1.2 Hz, 1H, ArH),
7.31–7.26 (m, 1H, ArH), 7.01–6.95 (m, 2H, ArH), 4.48 (t, J = 9.6 Hz, 2H, OCH2),
3.98 (t, J = 8.0 Hz, 2H, NCH2), 3.86 (s, 3H, ArOCH3); 13C NMR (100 MHz,
CDCl3), (δ, ppm): 157.5 (ArC), 155.0 (C=O), 129.0 (ArC), 128.5 (ArC), 126.2
(ArC), 121.1 (ArC), 112.1 (ArC), 62.6 (OCH2), 55.8 (OCH3), 47.1 (NCH2).
3‑(3‑methoxyphenyl)oxazolidin‑2‑one (22a) [48] White solid; mp 74.0–76.0 °C; IR
(KBr, ν, cm−1): 1750 (C=O), 1602 (C=C), 1499 (C=C), 1409 (C=C), 1225 (C–N),
1
1125 (C–N), 1040 (C–O), 760 (C–H); H NMR (400 MHz, CDCl3), (δ, ppm):
7.29–7.25 (m, 2H, ArH), 7.05–7.03 (m, 1H, ArH), 6.71–6.68 (m, 1H, ArH), 4.48
(t, J = 7.6 Hz, 2H, OCH2), 4.05 (t, J = 8.0 Hz, 2H, NCH2), 3.82 (s, 3H, ArOCH3);
13C NMR (100 MHz, CDCl3), (δ, ppm): 160.3 (ArC), 155.3 (C=O), 139.6 (ArC),
129.9 (ArC), 110.4 (ArC), 109.7 (ArC), 104.6 (ArC), 61.4 (OCH2), 55.5 (OCH3),
45.4 (NCH2).
3‑(4‑methoxyphenyl)oxazolidin‑2‑one (23a) [48] White solid; mp 109.0–111.0 °C;
IR (KBr, ν, cm−1): 2925 (C–H), 1722 (C=O), 1515 (C=C), 1377 (C=C), 1289
1
(C–N), 1223 (C–N), 1132 (C–N), 1027 (C–O), 994 (C–O), 829 (C–H); H NMR
(400 MHz, CDCl3), (δ, ppm): 7.44 (d, J = 8.8 Hz, 2H, ArH), 6.91 (d, J = 8.8 Hz,
2H, ArH), 4.46 (t, J = 7.2 Hz, 2H, OCH2), 4.02 (t, J = 8.4 Hz, 2H, NCH2), 3.80 (s,
1 3

Synthesis of N‑aryl‑2‑oxazolidinones from cyclic carbonates…
3H, ArOCH3); 13C NMR (100 MHz, CDCl3), (δ, ppm): 156.5 (ArC), 155.7 (C=O),
131.6 (ArC), 120.4 (ArC), 114.4 (ArC), 61.4 (OCH2), 55.6 (OCH3), 45.9 (NCH2).
3‑(2,6‑dimethylphenyl)oxazolidin‑2‑one (24a) [50] White solid; mp 136.5–
137.0 °C; IR (KBr, ν, cm−1): 1748 (C=O), 1594 (C=C), 1482 (C=C), 1407 (C=C),
1
1292 (C–N), 1221 (C–N), 1127 (C–N), 1038 (C–O), 958 (C–O), 744 (C–H); H
NMR (400 MHz, CDCl3), (δ, ppm): 7.19–7.10 (m, 3H, ArH), 4.56 (t, J = 8.0 Hz,
2H, OCH2), 3.84 (t, J = 8.0 Hz, 2H, NCH2), 2.29 (s, 6H, 2 × ArCH3); 13C NMR
(100 MHz, CDCl3), (δ, ppm): 156.7 (C=O), 136.9 (ArC), 134.2 (ArC), 128.9 (ArC),
128.8 (ArC), 62.6 (OCH2), 46.3 (NCH2), 17.9 (2 × ArCH3).
3‑(4‑bromo‑2,6‑dimethylphenyl)oxazolidin‑2‑one (25a) White solid; mp 160.0–
164.0 °C; IR (KBr, ν, cm−1): 1748 (C=O), 1576 (C=C), 1481 (C=C), 1406 (C=C),
1296 (C–N), 1252 (C–N), 1130 (C–N), 1037 (C–O), 949 (C–O), 913 (C–H), 858
(C–H), 744 (C–H); 1H NMR (400 MHz, CDCl3), (δ, ppm): 7.27 (s, 2H, ArH), 4.56
(t, J = 8.4 Hz, 2H, OCH2), 3.81 (t, J = 8.4 Hz, 2H, NCH2), 2.26 (s, 6H, 2 × ArCH3);
13C NMR (100 MHz, CDCl3), (δ, ppm): 156.5 (C=O), 139.1 (ArC), 133.4 (ArC),
131.8 (ArC), 122.5 (ArC), 62.6 (OCH2), 46.1 (NCH2), 17.8 (2 × ArCH3); HRMS
(ESI) m/z: calculated for C11H12BrNO2Na [M + Na]+: 291.9949; found: 291.9922.
3‑(2,6‑diethylphenyl)oxazolidin‑2‑one (26a) [50] Yellow oil; IR (KBr, ν, cm−1):
1749 (C=O), 1465 (C=C), 1410 (C=C), 1296 (C–N), 1220 (C–N), 1127 (C–N),
1
1036 (C–O), 983 (C–O), 807 (C–H), 760 (C–H); H NMR (400 MHz, CDCl3),
(δ, ppm): 7.28 (t, J = 7.6 Hz, 1H, ArH), 7.16 (t, J = 7.2 Hz, 2H, ArH), 4.51 (t,
J = 8.0 Hz, 2H, OCH2), 3.87 (t, J = 8.4 Hz, 2H, NCH2), 2.67–2.61 (m, 2H, ArCH2),
2.59–2.51 (m, 2H, ArCH2), 1.27–1.23 (t, J = 7.6 Hz, 6H, 2 × ArCH3); 13C NMR
(100 MHz, CDCl3), (δ, ppm): 157.2 (C = O), 142.6 (ArC), 132.9 (ArC), 129.1
(ArC), 126.7 (ArC), 62.4 (OCH2), 47.6 (NCH2), 24.1 (2 × ArCH2), 14.6 (2 × CH3).
3‑(naphthalen‑1‑yl)oxazolidin‑2‑one (27a) [46] Gray solid; mp 129.5–130.0 °C;
IR (KBr, ν, cm−1): 1734 (C=O), 1594 (C=C), 1508 (C=C), 1488 (C=C), 1416
(C=C), 1297 (C–N), 1235 (C–N), 1140 (C–N), 1039 (C–O), 934 (C–O), 778 (C–H),
736 (C–H); 1H NMR (400 MHz, CDCl3), (δ, ppm): 7.91–7.85 (m, 3H, ArH), 7.59–
7.47 (m, 4H, ArH), 4.64(t, J = 8.0 Hz, 2H, OCH2), 4.09 (t, J = 7.6 Hz, 2H, NCH2);
13C NMR (100 MHz, CDCl3), (δ, ppm): 157.6 (C=O), 134.7 (ArC), 134.1 (ArC),
130.0 (ArC), 128.9 (ArC), 128.8 (ArC), 127.1 (ArC), 126.7 (ArC), 125.7 (ArC),
124.7 (ArC), 122.4 (ArC), 62.6 (OCH2), 48.2 (NCH2).
3‑(naphthalen‑2‑yl)oxazolidin‑2‑one (28a) [45] Gray solid; mp 210.0–211.0 °C;
IR (KBr, ν, cm−1): 1736 (C=O), 1600 (C=C), 1509 (C=C), 1473 (C=C), 1404
(C=C), 1310 (C–N), 1220 (C–N), 1112 (C–N), 1048 (C–O), 1008 (C–O), 748
(C–H), 708 (C–H); 1H NMR (400 MHz, CDCl3), (δ, ppm): 7.97 (d, J = 8.0 Hz, 1H,
ArH), 7.87–7.79 (m, 3H, ArH), 7.71 (s, 1H, ArH), 7.50–7.41 (m, 2H, ArH), 4.52
(t, J = 7.6 Hz, 2H, OCH2), 4.17 (t, J = 8.0 Hz, 2H, NCH2); 13C NMR (100 MHz,
CDCl3), (δ, ppm): 155.5 (C=O), 136.1 (ArC), 133.6 (ArC), 130.4 (ArC), 129.1
1 3

C. Mei et al.
(ArC), 127.7 (ArC), 127.6 (ArC), 126.8 (ArC), 125.4 (ArC), 118.4 (ArC), 114.9
(ArC), 61.5 (OCH2), 45.6 (NCH2).
5‑methyl‑3‑phenyloxazolidin‑2‑one (29a) [46] White solid; mp 79.5–81.5 °C; IR
(KBr, ν, cm−1): 1748 (C=O), 1600 (C=C), 1505 (C=C), 1407 (C=C), 1308 (C–N),
1217 (C–N), 1119 (C–N), 1082 (C–O), 981 (C–O), 760 (C–H); 1H NMR (400 MHz,
CDCl3), (δ, ppm): 7.55–7.52 (m, 2H, ArH), 7.39–7.35 (m, 2H, ArH), 7.15–7.11
(m, 1H, ArH), 4.83–4.75 (m, 1H, OCH), 4.12 (t, J = 8.4 Hz, 1H, NCH2), 3.63
(t, J = 7.6 Hz, 1H, NCH2), 1.54 (d, J = 6.4 Hz, 3H, CH3); 13C NMR (100 MHz,
CDCl3), (δ, ppm): 155.0 (C=O), 138.5 (ArC), 129.2 (ArC), 124.1 (ArC), 118.3
(ArC), 69.7 (OCH), 52.0 (NCH2), 20.9 (CH3).
3‑(4‑chlorophenyl)‑5‑methyloxazolidin‑2‑one (30a) [45] Yellow oil; IR (KBr, ν,
cm−1): 1707 (C=O), 1600 (C=C), 1541 (C=C), 1495 (C=C), 1404 (C=C), 1308
1
(C–N), 1231 (C–N), 1069 (C–O), 913 (C–O), 828 (C–H); H NMR (400 MHz,
CDCl3), (δ, ppm): 7.34–7.25 (m, 4H, ArH), 4.23–4.20 (m, 1H, OCH), 4.11–4.00 (m,
2H, NCH2), 1.25 (d, J = 1.6 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3), (δ, ppm):
153.6 (C=O), 136.3 (ArC), 131.1 (ArC), 129.2 (ArC), 120.1 (ArC), 66.5 (OCH),
29.8 (NCH2), 19.3 (CH3).
5‑methyl‑3‑(p‑tolyl)oxazolidin‑2‑one (31a) [51] White solid; mp 65.0–66.0 °C; IR
(KBr, ν, cm−1): 1750 (C=O), 1508 (C=C), 1418 (C=C), 1297 (C–N), 1227 (CON),
1048 (C–O), 942 (C–O), 807 (C–H); 1H NMR (400 MHz, CDCl3), (δ, ppm): 7.24–
7.21 (m, 2H, ArH), 7.13 (t, J = 9.2 Hz, 2H, ArH), 4.21 (dd, J = 10.4 Hz, J = 2.4 Hz,
1H, OCH), 3.73–3.63 (m, 1H, NCH2), 3.32 (d, J = 7.6 Hz, 3H, ArCH3), 1.31–1.23
(m, 3H, CH3); 13C NMR (100 MHz, CDCl3), (δ, ppm): 153.9 (C=O), 135.1 (ArC),
133.4 (ArC), 129.6 (ArC), 119.2 (ArC), 70.4 (OCH), 66.5 (NCH2), 20.9 (ArCH3),
19.3 (CH3).
5‑phenyl‑3‑(p‑tolyl)oxazolidin‑2‑one (32a) [52] Yellow oil; IR (KBr, ν, cm−1):
1749 (C=O), 1540 (C=C), 1508 (C=C), 1418 (C=C), 1298 (C–N), 1227 (C–N),
1047 (C–O), 940 (C–O), 857 (C–H); 1H NMR (400 MHz, CDCl3), (δ, ppm): 7.82–
7.77 (m, 5H, ArH), 7.68 (d, J = 9.2 Hz, 2H, ArH), 7.53 (d, J = 8.4 Hz, 2H, ArH),
6.29 (dd, J = 7.2 Hz, J = 4.0 Hz, 1H, OCH), 4.36–4.32 (m, 2H, NCH2), 2.73 (s, 3H,
ArCH3); 13C NMR (100 MHz, CDCl3), (δ, ppm): 153.4 (C=O), 137.3 (ArC), 135.1
(ArC), 133.4 (ArC), 129.7 (ArC), 128.8 (ArC), 128.6 (ArC), 126.7 (ArC), 126.3
(ArC), 66.4 (OCH), 29.8 (NCH2), 20.9 (CH3).
5‑methyl‑3‑(naphthalen‑1‑yl)oxazolidin‑2‑one (33a) [41] White solid; mp 140.0–
142.0 °C; IR (KBr, ν, cm−1): 1748 (C=O), 1596 (C=C), 1510 (C=C), 1466 (C=C),
1417 (C=C), 1299 (C–N), 1228 (C–N), 1144 (C–N), 1050 (C–O), 744 (C–H), 707
1
(C–H); H NMR (400 MHz, CDCl3), (δ, ppm): 7.92–7.85 (m, 3H, ArH), 7.59–
7.46 (m, 4H, ArH), 5.01–5.93 (m, 1H, OCH), 4.16 (t, J = 8.8 Hz, 1H, NCH2),
3.69 (t, J = 4.4 Hz, 1H, NCH2), 1.65 (d, J = 6.4 Hz, 3H, –OCHCH3); 13C NMR
(100 MHz, CDCl3), (δ, ppm): 157.0 (C=O), 134.4 (ArC), 133.9 (ArC), 129.7 (ArC),
1 3

Synthesis of N‑aryl‑2‑oxazolidinones from cyclic carbonates…
128.4 (ArC), 126.7 (ArC), 126.3 (ArC), 125.4 (ArC), 124.3 (ArC), 122.2 (ArC),
70.8(OCH), 55.4 (NCH2), 20.5 (CH3).
Acknowledgements We are grateful to the National Natural Science Foundation of China (NSFC
21571087), Major Projects of Natural Science Research in Jiangsu Province (15KJA150004), PAPD and
TAPP of Jiangsu Higher Education Institutions, and the State Key Laboratory of Inorganic Synthesis and
Preparative Chemistry at Jilin University (2016-01) for fnancial support.
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