Synthesis of Oxazolidinones and Derivatives through Three-Component Fixation of Carbon Dioxide

Article abstract of DOI:10.1002/cctc.201800142

An effective three-component fixation of atmospheric CO₂ with readily available 1,2-dichloroethane and aromatic amine toward oxazolidinones catalyzed by in situ NHC was developed. The reaction occurred in good to excellent yields with good gene

Full text of DOI:10.1002/cctc.201800142

Accepted Article
Title: Synthesis of Oxazolidinones and Derivatives through Three-
Component Fixation of Carbon Dioxide
Authors: Congmin Mei, Yibo Zhao, Qianwei Chen, Changsheng Cao,
Guangsheng Pang, and Yanhui Shi
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Synthesis of Oxazolidinones and Derivatives through Three-
Component Fixation of Carbon Dioxide
Congmin Mei,[a] Yibo Zhao,[a] Qianwei Chen,[a] Changsheng Cao,*[a] Guangsheng Pang,[b] Yanhui Shi*[a]
Abstract: An effective three-component fixation of atmospheric CO2
with readily available dichloroethane and aromatic amine toward
oxazolidinones catalyzed by in-situ NHC was developed. The
reaction occurred in good to excellent yields with good generality
and wide functional group tolerance, including challenging steric
hindered substituted-dichloroethane (e.g. 1,2-dichloropropane and
2,3-dichlorobutane). The catalytic system is not sensitive to air and
moisture, and high yield of oxazolidinone was achieved even with
about 0.3 atm of pressure of carbon dioxide. The mechanistic study
suggests that the reaction catalyze by in-situ NHC via CO2-NHC
adduct, 1-n-butyl-3-methylimidazolium-2-carboxylate as intermediate
and aminochloride involves in reaction pathways. The catalyst can
be recycled for at least 3 times without obvious loss of catalytic
activity. The protocol is also effective to prepare six-membered 3-
aryl-1,3-oxazinan-2-one and even seven-membered 3-aryl-1,3-
oxazepan-2-one, when dichloropropane and dichlorobutane was
employed.
catalyst,[26,39] ect. To avoid the tedious process of preparation
and isolation of starting materials, it would be better to design a
multi-component reaction using readily available substrates.
Recently,
a
few 3-component reactions to prepare
oxazolidinones from CO2 have reported (Scheme 1).[40-45] The 3-
component reaction of amines, ethylene oxide with CO2 was
explored mostly and amino alcohols, phenyl isocyanate and
cyclic carbonates have been proposed as intermediate in the
catalytic cycle.[40-44] Besides, there is one report about 3-
component reaction of 1,2-dibromoethane, anilines with CO2.[45]
Even though this reaction carried out under mild conditions, only
active and less hindered dibromoalkanes was investigated. It is
interesting to develop
a new efficient, economical and
environmentally friendly three-component reaction with good
generality. Herein, we demonstrate for the first time to prepare
oxazolidinones and derivatives through three-component
reaction of carbon dioxide with cheap dichloroalkanes and
aromatic
amines
catalyzed
by
readily
available
[Bmim]OAc/Cs2CO3/Bu4NBr under solvent-free conditions at 1
atm pressure of CO2.
Introduction
Due to environmental and economical concerns, the
development of efficient methods to transform carbon dioxide
(CO2), a naturally abundant and nontoxic carbon resource, into
valuable chemicals has attracted increasing attention for a long
time.[1,2] Despite the synthetic challenge owing to thermodynamic
stability and kinetic inertness of CO2, a variety of efficient CO2
transformations has been discovered in the past decades. CO2
has been successfully converted to methanol,[3,4] urethanes,[5,6]
formic acid,[7,8] dimethyl carbonate,[9,10] cyclic carbonates,[11–17]
carbamates[18,19]
and
others.[14–17,20]
Among
these
transformations, the direct preparation of oxazolidinones from
CO2 has attracted a significant attention as they have showed
pharmacological activities and been used in the treatment for
bacterial infection and depression.[21–25] However, a number of
the existing methods have to use prefunctionalized substrates,
such as allyl or propargyl amine,[26–32] aziridines[33–37] or amino
Scheme 1. Three component reactions for the synthesis of oxazolidinones
epoxides,[38] which requires tedious synthetic steps to prepare. Results and Discussion
In addition, there are other limitations in those above methods,
such as a narrow reaction scope,[27,29,31] low selectivity,[34,35]
multiple isomeric products,[33,37] and complex and unrecycled
Evaluating the reaction conditions
[a]
[b]
C. Mei, Y. Zhao, Q. Chen, Prof. C. Cao, Prof. Y. Shi
School of Chemistry and Material Science and Jiangsu Key
Laboratory of Green Synthetic Chemistry for Functional Materials
Jiangsu Normal University, Xuzhou, Jiangsu 221116, PR China
E-mail: yhshi@jsnu.edu.cn, Fax: (+86)56183500349
Prof. G. Pang
State Key Laboratory of Inorganic Synthesis and Preparative
Chemistry
College of Chemistry
Effect of different imidazolium salts, quaternary
ammonium salts and bases
The catalytic activity of [Bmim]OAc/Cs2CO3 was initially
investigated in the reaction of CO2, aniline and 1,2-
dichloroethane at 1 atm of CO2 under solvent-free conditions
(Table 1, entry 1). 3-Phenyloxazolidin-2-one was obtained in
65% of yield when the reaction was carried out at 80 °C for 12 h.
As no solvent was employed in the reaction and the reaction
involves gas, liquid and solid phases, we assume that the
Jilin University, Changchun, Jilin 130012, PR China
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10.1002/cctc.201800142
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presence of phase transfer catalyst might improve the reaction
yield. Therefore, the effect of adding quaternary ammonium salts
Bu4NX (X = PF6, Cl, Br) was investigated (Table 1, entries 2–4).
The results showed that Bu4NBr would promote the reaction
significantly, leading to 95% yield of product.
The different bases were also tested (Table 1, entries 4–8), and
the results showed that Cs2CO3 was the best base used in the
all tested bases (95% yield) and the other bases only gave 6–
17% yields of the product. Additionally, the different imidazolium
salts were explored as well (Table 1, entries 4 and 9–12). The
results indicated that [Bmim]OAc showed the best catalytic
activity, whereas, the other tested imidazolium salts provided
only 21–27% yields of the product.
9
[Bmim]Br (50)
[Bmim]Cl (50)
[Emim]Br (50)
[Hmim]Br (50)
[Bmim]OAc (50)
[Bmim]OAc (50)
[Bmim]OAc (50)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (1)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (5)
6
6
6
6
6
6
6
6
23
27
25
21
67
96
55
10
11
12
13
14
15
16
Bu4NBr (15)
Bu4NBr (10)
Cs2CO3
(0.5)
[Bmim]OAc (50)
Bu4NBr (10)
28
The influence of the amount of Bu4NBr, Cs2CO3, [Bmim]OAc and
dichloroethane on the reaction was investigated as well.
Decreasing the amount of Bu4NBr to 5 mol% would lead largely
decreasing the yield to 67% (Table 1, entry 13), whereas,
increasing the amount of Bu4NBr to 15 mol% only slightly
increase the yield (Table 1, entry 14). Furthermore, the amount
of Cs2CO3 affected the yield significantly. The highest yield of
the product was observed with 2 equivalent of Cs2CO3, whereas,
less amount of Cs2CO3 would lead to less formation of the
product (Table 1, entries 4 and 15–16). Largely reducing the
amount of [Bmim]OAc from 50 to 10 mol% would not have an
obvious impact on the yield, however, only 67% of the product
was observed when 5 mol% of [Bmim]OAc was used (Table 1,
entires 4 and 17–19). The equivalent of dichloroethane used
also has effect on the reaction (Table 1, entires 20–23). The
yield of the product increased gradually when equivalent of
dichloroethane was increased from 4 to 7, and then no much
change was observed with more dichloroethane added.
17
18
19
20
21
22
23
[Bmim]OAc (20)
[Bmim]OAc (10)
[Bmim]OAc (5)
[Bmim]OAc (10)
[Bmim]OAc (10)
[Bmim]OAc (10)
[Bmim]OAc (10)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Cs2CO3 (2)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
6
6
6
4
5
7
8
95
95
67
60
88
97
97
[a] Reaction conditions: CO2 (1 atm), aniline (1 mmol, 91μL), 1,2-dichloroethane (4–8
mmol), imidazolium salt (0.05–0.5 mmol), base (0.5–2 mmol) and additive (0.05–0.15
mmol). [b] GC yield, using dodecane as internal standard and the average of two runs.
Effect of reaction time and temperature
Table 1 Screening of imidazolium salts, bases and ammonium salts for the
cycloaddition reaction of CO2 to 3-phenyl-2-oxazolidinones
In addition, the effects of time and temperature on the reaction
were studied as well (Fig. 1). As shown in Fig. 1(a), the yield of
3-phenyl-2-oxazolidinone increased dramatically with the rise in
temperature from 50 to 70 oC, and leveled off with further rise in
temperature from 70 to 90 oC. As shown in Fig. 1(b), the
reaction went to completion after 4 h and no increase of yield
was happened after 4 h.
1,2-
Imidazolium salt
(mol%)
Additive
(mol%)
Dichlor
oethan
e (eq.)
Yield
(%)[b]
100
80
60
40
20
0
(a)
100 (b)
Entry[a]
Base (eq.)
80
60
40
20
1
2
[Bmim]OAc (50)
[Bmim]OAc (50)
Cs2CO3 (2)
Cs2CO3 (2)
-
6
6
65
60
Bu4NPF6
(10)
0
2
50
60
70
80
90
3
4
5
6
Temp (oC)
Time (h)
3
4
5
6
7
8
[Bmim]OAc (50)
[Bmim]OAc (50)
[Bmim]OAc (50)
[Bmim]OAc (50)
[Bmim]OAc (50)
[Bmim]OAc (50)
Cs2CO3 (2)
Cs2CO3 (2)
Na2CO3 (2)
NaHCO3 (2)
K2CO3 (2)
Bu4NCl (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
Bu4NBr (10)
6
6
6
6
6
6
71
95
12
6
Fig. 1 Effect of reaction temperature (a) and time (b) on the yield of 3-phenyl-
2-oxazolidinone.
Reaction conditions: CO2 (1 atm), aniline (1 mmol, 91 μL), 1,2-dichloroethane (7
mmol, 560 μL), [Bmim]OAc (0.1 mmol, 19.8mg), Cs2CO3 (2 mmol, 0.65 g) and
Bu4NBr (0.1 mmol, 32.2 mg), (a) 50–90 °C, 12 h (b) 70 °C, 2–6 h.
17
10
NaOAc (2)
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Therefore, the optimal conditions for the reaction is 10 mol% of
Bu4NBr, 10 mol% of [Bmim]OAc and 2 equivalent of Cs2CO3,
with 7 equivalent of dichloroethane at 70 ºC for 4 h.
Synthesis of 3-aryl-2-oxzaolidiones
The general applicability of catalytic system was further tested
for various aromatic amines under optimal conditions (Table 2,
compounds 1–37).
Scope of the reaction
Table 2 Synthesis of 3-aryl-2-oxazolidinones and derivatives
Reaction conditions: CO2 (1 atm), aryl amines (1 mmol), dichloroalkane (7 mmol), [Bmim]OAc (0.1 mmol, 19.8 mg), Bu4NBr (0.1 mmol, 32.2 mg), Cs2CO3 (2 mmol, 0.65 g),
70 °C, 4 h. 38-44, 90 °C, 12 h.
Table 3 Synthesis of 3-aryl-1,3-oxazinan-2-one and 3-aryl-1,3-oxazepan-2-one
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Reaction conditions: CO2 (1 atm), aryl amines (1 mmol), dichloroalkane (7 mmol), [Bmim]OAc (0.1 mmol, 19.8 mg), Bu4NBr (0.1 mmol, 32.2 mg), Cs2CO3 (2 mmol, 0.65 g), at
90 °C for 6 h. 64–69, 90 °C for 12 h.
The results showed that all the tested aromatic amines,
including various substituted anilines, naphthalenyl amines, 1-
phenyl-1H-pyrazol-5-amine, benzo[d]thiazol-2-amine and 3-
methylisoxazol-5-amine were applicable in this system, and can
be successfully converted to the corresponding 3-aryl-2-
oxazolidinones in good to excellent yields.There is not obvious
electronic effect for the reaction as the electron withdrawing
groups or electron-donating groups have insignificant effect on
the reaction yield. However, the steric hindrance has some
effect on the reaction. For example, anilines with substituent in
ortho-position led to low yield of the product compared to its
analogue bearing substituents in meta- or para-position (Table 2,
compounds 9–11 and 12–14), moreover, the yield decreased
with enlarging the size of substituent on the substrate (Table 2,
compounds 25 and 27–28).Notably, 3-fluoro-4-morpholinoaniline
(compound 37), a motif of antibiotic Linezolid has been
successfully synthesized in 96% yield in one-step using this
protocol. Moreover, steric hindered mono- and di-substituted
1,2-dichloroethane were investigated in this catalytic system as
well (Table 2, compounds 38–44). The results (Table 2,
Synthesis of 3-aryl-1,3-oxazinan-2-one and 3-aryl-1,3-
oxazepan-2-one
Furthermore, it is interesting to explore if this protocol would
extend to prepare cyclic carbamate with larger membered ring
via replacement of 1,2-dichloroethane by 1,3-dichloropropane,
1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane or
1,10-dichlorodecane. It was found that the reaction proceeded
smoothly with 1,3-dichloropropane and provided six-membered
3-aryl-1,3-oxazinan-2-one bearing diverse substituted groups
with different electronic and steric properties in good to excellent
yield (Table 3, compounds 45–63). The seven-membered 3-aryl-
1,3-oxazepan-2-one was also formed when 1,4-dichlorobutane
was employed, but in low yield (Table 3, compounds 64–66,
22%–35%). However, in the case of 1,5-dichloropentane, 1,6-
dichlorohexane and 1,10-dichlorodecane, only corresponding
acyclic linear carbamate was obtained due to the ring stain
causing by the longer chain (Table 3, compounds 67–69).
compounds 38–42) showed that 1,2-dichloropropane,
a
unsymmetrical mono-substituted dichloroethane were applicable
in protocol, however there is no regioselectivity for the products,
leading to the formation of 5-methyl-3-aryloxazolidin-2-one and
4-methyl-3-aryloxazolidin-2-one simultaneously. The total yield
of the two products could be achieved to about 70%. The
Effect of impurity and pressure of CO2
It is more practical if the low purity and low pressure of CO2
might be applied in the protocol. Firstly, the performance of the
catalytic system in the CO2 containing 50% (v%) of air was
tested, the result indicated that using the amount of air had very
little influence on catalytic activity, leading 95% of yield product
(Table 4, entry 1). Secondly, CO2 contaminating with some
amount of water (1, 10, 50 and 100 mol%) was investigated
(Table 4, entries 2-5) and less than 50 mol% amount of water
would not affect the catalytic activity of this catalytic system very
much (Table 4, entries 2-4). Even though 100 mol% of water
was introduced in the reaction, the product was still obtained in
81% of yield (Table 4, entry 5). Lastly, using less than 1 atm of
partial pressure of CO2 (about 0.50 and 0.33 atm) was explored
reaction with more steric hindered 2,3-dichlorobutane,
a
symmetrical di-substituted 1,2-dichloroethane went sluggishly,
and only afforded corresponding 4,5-dimethyl-3-aryloxazolidin-2-
one in 30–40% of yield (Table 2, compounds 43–44). It is worth
to note that the protocol has good tolerance for various
functional groups, such as CN, F, CF3, Cl, Br, NO2, OMe, COMe,
CH3CONH etc, which makes it possible for further
transformation.
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(Table 4, entries 6-7). It was found that low initial partial
pressure of CO2 had very little influence on the yield of product
as well. The results showed that a good yield could be achieved
with a partial pressure of 0.50 (97%) and even 0.33 atm (90%)
of CO2. The control experiment using cesium carbonate in the
absence of carbon dioxide indicated that the CO2 moiety in 3-
phenyl-2-oxazolidinone comes from carbon dioxide, not from
cesium carbonate, as no 3-phenyl-2-oxazolidinone was
observed in the reaction (Table 4, entry 8).
To compare activity of the recovered catalyst with the original
one, the conversion of aniline vs time was observed for the
different recycling runs (Fig. 3). From the result, we can see that
the initial rate of the first run is quite slower than that of the
second and third runs, whereas, the rate is quite similar for 2nd
and 3rd runs, indicating the recovered catalyst is more active
than the original precatalyst. To understand the reason, the
composition of recovered catalyst system was analyzed. 1H
NMR spectrum (Supporting Information) shows the signals
corresponding to the protons of 1-n-butyl-3-methylimidazolium-
2-carboxylate ([Bmim]-CO2),[46] a N-heterocylic carbene(NHC)-
CO2 adduct, which should be formed from the reaction of
[Bmim]OAc with CO2 in the presence of Cs2CO3, and the result
is further confirmed by HRMS [HRMS (ESI) for m/z: calcd. For
[([Bmim]-CO2)-H]+ C9H13N2O2: 181.0977; found: 181.0970.].
Furthermore, the presence of tetrabutylammonium bromide was
detected by 1H NMR. pH value of the recycled catalyst is around
9 indicating that the presence of cesium carbonate in the system.
Therefore, the composition of the recycle catalyst is [Bmim]-
CO2/Cs2CO3/Bu4NBr, which is a little different from original
[Bmim]OAc/ Cs2CO3/Bu4NBr.
Table 4 Effect of impurity and pressure of CO2 on the reaction
Entry[a]
Air (v%)
1
50
-
2
-
3
-
4
-
5
-
6
-
7
8[c]
-
-
-
H2O (mol%)
Partial PCO2 (atm)
GC Yield (%)
1
10
1
50
1
100
1
-
-
0.5
95
1
0.5[b]
97
0.33[b]
90
-
As NHC-CO2 adduct has been found wide application in
catalysis,[47-54] after its first isolation by Louie and coworkers,[55]
we assume that NHC-CO2 adduct probably involved in the
catalytic process and the activation time to generate NHC-CO2
in the 1st run causes the low initial rate. This assumption is
further confirmed in the mechanism study.
99
99
93
81
0
[a] Reaction conditions: CO2 (1–0.5 atm), aniline (1 mmol, 91μL), 1,2-dichloroethane (7
mmol, 560 μL), [Bmim]OAc (0.1 mmol, 19.8 mg), Bu4NBr (0.1 mmol, 32.2 mg), H2O
(0-1 mmol)) and Cs2CO3 (2 mmol, 0.65 g), 70 °C, 4 h. [b] the mixture of N2 and CO2. [c]
The control reaction.
Recycling of the catalyst
The recovery and recycle of catalyst is one of the main ideas of
green chemistry, so the reusability of the catalyst was examined.
The yields of product were checked in recycle 1 to recycle 5
(99%, 97%, 94%, 89%, 80%), and the results were shown in Fig.
2. The results indicated that the recovered catalyst could be
reused at least 3 times with little loss of the catalytic activity.
Fig. 3 Kinetic curves (conversion of aniline vs reaction time).
Reaction conditions: CO2 (1 atm), aniline (1 mmol, 91μL), 1,2-dichloroethane (7
mmol, 560 μL), [Bmim]OAc (0.5 mmol, 99 mg), Bu4NBr (0.1 mmol, 32.2 mg) and
Cs2CO3 (2 mmol, 0.65 g), 70 °C, 0.5–4 h.
Study of the reaction mechanism
To understand the reaction mechanism, a few control reactions
were carried out as shown in Scheme 2. Reaction 1 revealed
that [Bmim]OAc would not catalyze the reaction, and only 3% of
the product was detected when [Bmim]OAc/Bu4NBr was used
(reaction 2), indicating that the formation of NHC is essential for
the reaction. In the reaction mixture, N-(2-chloroethyl)aniline was
detected by GC-MS, and 90% yield of N-(2-chloroethyl)aniline
was isolated if the reaction was carried out in the absence of
CO2 (reaction 3). This suggests that N-(2-chloroethyl)aniline is
Fig. 2 Recycling of the catalyst.
Reaction conditions: CO2 (1 atm), aniline (1 mmol, 91μL), 1,2-dichloroethane (7
mmol, 560 μL), [Bmim]OAc (0.5 mmol, 99 mg), Bu4NBr (0.1 mmol, 32.2 mg) and
Cs2CO3 (2 mmol, 0.65 g), 70 °C, 4 h.
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the intermediate of the reaction. The control reaction 4 showed
that N-(2-chloroethyl)aniline further reacted with CO2, giving 3-
phenyl-2-oxazolidinones in 92% yield. The direct carboxylative
cyclization of vicinal haloamine[56] and halohydrin[57–59] with CO2
to unsubstituted 2-oxazolidinone and cyclic carbonates are
known, but with only very limited substrate scope, and some
reaction required high pressure of CO2 (20 atm).[58]
The
performance
of
NHC-CO2
adduct,
1-n-butyl-3-
methylimidazolium-2-carboxylate was investigated in reaction 5.
The result showed that 95% of 3-phenyl-2-oxazolidinone was
obtained,
which is
comparable to the result
of
Bu4NBr/Cs2CO3/[Bmim]OAc, indicating that NHC-CO2 adduct
would involve in the catalytic process and catalyze the reaction.
Scheme 3 The proposed reaction mechanism
Conclusions
In summary, an efficient approach for the preparation of
oxazolidinones and derivatives from 1,2-dichloroethane
(unsubstituted, mono and di-substituted), 1,3-dichloropropane,
or 1,4-dichlorobutane and aromatic amine with CO2 (1 atm)
under mild conditions catalyzed by NHC generated in-site has
been developed. The approach has good generality and
tolerates various functional groups, giving the products in good
yields. The contamination of CO2 with water and air has little
effect on the catalytic system and the decreasing pressure of
CO2 to about 0.33 atm does not affect the reaction significantly.
Compared with the existing methods in the literature, this
method has the advantages of mild reaction conditions, ready
available substrates and catalyst, easy separation of product
and recyclability of the catalyst. This also makes this method the
most attractive alternative to the synthesis of 3-aryl-2-
Scheme 2 The control reactions
oxzaolidiones,
oxazepan-2-ones.
3-aryl-1,3-oxazinan-2-one
and
3-aryl-1,3-
Based on these results, we propose the following mechanism for
the reaction (Scheme 3). N-(2-chloroethyl)aniline is generated
by the nucleophilic substitution reaction of aniline to 1,2-
dichloroethane, meanwhile, NHC-CO2 adduct is formed thought
the reaction of NHC formed in-situ with CO2. Then, the
nucleophilic substitution reaction of NHC-CO2 to the N-(2-
chloroethyl)aniline gives an amino ester, which could cyclize to
result in the formation of 3-phenyl-2-oxazolidinone and
regenerate NHC. From the catalytic cycle, we can see that NHC
is the real catalyst and NHC-CO2 is the intermediate in the
reaction. The direct cyclization of haloamine and halohydrin with
CO2 is under different mechanism, most likely via the formation
of carbamate anion or alkoxide anion.[56,57]
Experimental Section
General information
All substrates and reagents were purchased from commercial sources
and used as received. The aryl amines (> 97%) were purchased from
Energy Chemical. CO2 (99.99%) was purchased from Xuzhou Special
Gases Factory. Deuterated NMR solvents were purchased from
Cambridge Isotope Laboratorise, Inc. All other chemicals were analytical
grade and were supplied by Sinopharm Chemical Reagent Beijing Co.,
Ltd. 1H and 13C NMR spectra were recorded on Bruker AV400
spectrometer with chemical shift values relative to solvent residue. 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. GC-MS was performed on an Agilent 6890-5973N system
with electron ionization (EI) mass spectrometry. Analytic HPLC was
performed using an Agilent 1200 series chromatograph equipped with an
Eclipse XDB-C18 column.
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give the product as yellow oil. Yield: 88%.1H NMR (400 MHz, CDCl3): δ =
7.55 (d, J = 1.6 Hz, 1H), 7.44 (t, J = 2.0 Hz, 1H), 4.27 (t, J = 7.2 Hz, 3H),
4.04 (s, 3H), 1.86–1.79 (m, 2H), 1.37–1.28 (m, 2H), 0.88 (t, J = 7.2 Hz,
2H). 13C NMR (100 MHz, CDCl3): δ = 170.3, 136.0, 123.0, 121.6, 48.8,
35.8, 31.3, 18.5, 12.6. IR (KBr): ν = 1650 cm-1 (C=O).
General procedure for the synthesis of 3-aryl-2-
oxzaolidiones
[Bmim]OAc (0.1 mmol, 19.8 mg), Cs2CO3 (2 mmol, 0.65 g), Bu4NBr (0.1
mmol, 32.2 mg) and aromatic amine (1 mmol) were introduced to a 25
mL of Schlenk flask under air. The flask was purged with CO2 for three
times and 1,2-dichloroethane (7 mmol, 560 μL) was injected into the flask
by syringe. The reaction was replenished with CO2 balloon (4L) and
Kinetic experiment
o
stirred at 70 C for 4 h, after which time, 25 mL of water was added into
the reaction mixture. The organic layer was extracted with ethyl acetate
(3  10 mL). The combined organic phase was dried over Na2SO4 and
concentrated under reduced pressure. The residue was purified by flash
column chromatography on silica gel (petroleum ether/ethyl acetate =
10:1 as eluent). For the reaction under 0.5 or 0.33 atm of CO2, the
mixture of nitrogen and CO2 with volume ratio of 1:1 or 2:1 was used for
purging and reaction.
The procedure is the same as the recycling procedure with biphenyl
(1mmol) as internal standard. The reaction time is from 0.5 h, 1 h, 1.5 h,
2 h, 2.5 h, 3 h, 3.5 h and 4 h. The relative aniline versus biphenyl
concentration was monitored as a function of time by HPLC.
Data for the products
3-phenyloxazolidin-2-one (1):[60] White solid, m.p. 120.0–122.5 oC. 1H
NMR (400 MHz, CDCl3): δ = 7.56–7.53 (m, 2H), 7.44–7.37 (m, 2H),
7.17–7.13 (m, 2H), 4.50 (t, J = 7.6 Hz, 2H), 4.07 (t, J = 8.0 Hz, 2H). 13C
NMR (100 MHz, CDCl3): δ = 155.4, 138.4, 129.2, 124.2, 118.4, 61.4,
45.3. IR (KBr): ν = 1740 cm-1 (C=O).
General procedure for the synthesis of 3-aryl-1,3-
oxazinan-2-one
The procedure is the same as above.
1,3-dichloropropane (7 mmol, 660 μL), 90 oC for 6 h, and petroleum
ether/ethyl acetate = 5:1.
3-(4-ethylphenyl)oxazolidin-2-one (2):[61] White solid, m.p. 63.0–65.0 oC.
1H NMR (400 MHz, CDCl3): δ = 7.44–7.42 (m, 2H), 7.20 (d, J = 8.4 Hz,
2H), 4.46 (t, J = 8.0 Hz, 2H), 4.03 (t, J = 8.0 Hz, 2H), 2.63 (dd, J = 14.8
Hz, J = 7.6 Hz, 2H), 1.22 (t, J = 8.4 Hz, 3H). 13C NMR (100 MHz, CDCl3):
δ = 155.5, 140.3, 136.0, 128.5, 118.6, 61.4, 45.5, 28.3, 15.7. IR (KBr): ν
= 1748 cm-1 (C=O).
General procedure for the synthesis of 3-aryl-1,3-
oxazepan-2-one
o
1
3-(4-butylphenyl)oxazolidin-2-one (3): White solid, m.p. 69.5–73.5 C. H
NMR (400 MHz, CDCl3): δ = 7.44–7.41 (m, 2H), 7.18–7.16 (m, 2H), 4.45
(d, J = 7.6 Hz, 2H), 4.02 (d, J = 8.4 Hz, 2H), 2.58 (t, J = 3.6 Hz, 2H),
1.61–1.54 (m, 2H), 1.39–1.29 (m, 2H), 0.92 (t, J = 7.2 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ = 155.5, 138.9, 136.0, 129.0, 118.5, 61.4, 45.4, 35.0,
33.7, 22.3, 14.0. HRMS (ESI) m/z calcd. for C13H17NO2Na [M+Na]+:
242.1157; found: 242.1136. IR (KBr): ν = 1743 cm-1 (C=O).
The procedure is the same as above.
1,4-dichlorobutane (7 mmol, 780 μL), 90 oC for 12 h, and petroleum
ether/ethyl acetate = 10:1.
Recycling procedure of the catalytic system
3-(4-iodophenyl)oxazolidin-2-one (4):[62] White solid, m.p. 162.0–163.5 oC.
1H NMR (400 MHz, CDCl3): δ = 7.68–7.64 (m, 2H), 7.34–7.30 (m, 2H),
4.48 (t, J = 7.6 Hz, 2H), 4.02 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3): δ = 155.1, 138.2, 138.0, 120.0, 87.5, 61.4, 45.0. IR (KBr): ν =
1749 cm-1 (C=O).
[Bmim]OAc (0.5 mmol, 99 mg), Cs2CO3 (2 mmol, 0.65 g), Bu4NBr (0.1
mmol, 32.2 mg), and aniline (1 mmol, 91 μL) were added into a 25 mL of
Schlenk flask under air. The Schlenk flask was purged with CO2 for three
times, then 1,2-dichloroethane (7 mmol, 560 μL) was injected into the
flask by syringe. The reaction was replenished with CO2 balloon (4L) and
stirred at 70 oC for 4 h. The product was separated from the reaction
mixture through extraction with ethyl acetate (5  10 mL). The residue
was dried under vacuum to remove left ethyl acetate giving the recovered
catalyst. The new batch of 1,2-dichloroethane (7 mmol, 560 μL) and
aniline (1 mmol, 91 μL) were added, and then CO2 (4 L) was provided. A
second run of 4 h at 70 oC was performed. This operation was
continuously repeated.
3-(4-(trifluoromethyl)phenyl)oxazolidin-2-one (5):[62] White solid, m.p.
93.5–95.5 oC. 1H NMR (400 MHz, CDCl3): δ = 7.65 (dd, J = 20.0 Hz, J =
8.8 Hz, 4H), 4.53 (t, J = 7.6 Hz, 2H), 4.10 (t, J = 8.0 Hz, 2H). 13C NMR
(100 MHz, CDCl3): δ = 155.0, 141.3, 126.4 (q, J = 2.6 Hz), 126.3 (d, J =
32.8 Hz), 124.2 (d, J = 270.0 Hz), 117.8, 61.5, 45.1. IR (KBr): ν = 1740
cm-1 (C=O).
3-(4-cyano)oxazolidin-2-one (6):[63] White solid, m.p. 142.0–144.0 C. H
NMR (400 MHz, CDCl3): δ = 7.70–7.64 (m, 4H), 4.53 (t, J = 8.0 Hz, 2H),
4.09 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 154.7, 142.2,
133.3, 118.8, 118.0, 107.0, 61.5, 44.8, 29.8. IR (KBr): ν = 1740 cm-1
(C=O).
o
1
Preparation
carboxylate[46]
of
1-n-butyl-3-methylimidazolium-2-
To 40 mL of THF in an oven-dried Schlenk flask equipped with a
magnetic stir bar was added 1-n-butyl-3-methylimidazolium acetate
(0.198 g, 1 mmol) and tBuOK (0.134 g, 1.2 mmol) under nitrogen
atmosphere. The reaction was replenished with CO2 balloon (4L) and
stirred at room temperature for 5 h, after which time, the solvent was
removed by rotary evaporation and the residue was purified by column to
3-(4-acetylphenyl)oxazolidin-2-one (7):[36] White solid, m.p. 151.0–152.5
oC. 1H NMR (400 MHz, CDCl3): δ = 7.98–7.95 (m, 2H), 7.64–7.61 (m, 2H),
4.51 (t, J = 7.6 Hz, 2H), 4.10 (t, J = 8.8 Hz, 2H), 2.57 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 157.5, 154.7, 149.4, 132.8, 126.4, 124.2, 121.5,
121.4, 63.5, 45.1, 30.5. IR (KBr): ν = 1761 cm-1 (C=O).
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10.1002/cctc.201800142
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N-(4-(2-oxooxazolidin-3-yl)phenyl)acetamide (8): White solid, m.p.
110.0–112.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.56 (s, 2H), 7.26 (s,
2H), 4.50 (t, J = 8.0 Hz, 2H), 4.07 (t, J = 8.0 Hz, 2H), 2.18 (s, 1H), 1.57 (s,
3H). 13C NMR (100 MHz, CDCl3): δ = 156.9, 151.9, 129.7, 128.8, 125.8,
124.4, 62.8, 47.4, 29.8. HRMS (ESI) m/z: calcd. for [M+H]+ C11H13N2O3:
221.0926; found: 221.0925. IR (KBr): ν = 1801 cm-1 (C=O).
110.8 (d, J = 21.0 Hz), 105.8 (d, J = 27.0 Hz), 61.4, 45.2. IR (KBr): ν =
1739 cm-1 (C=O).
3-(4-fluorophenyl)oxazolidin-2-one (18):[61] White solid, m.p. 71.0–72.0 oC.
1H NMR (400 MHz, CDCl3): δ = 7.53–7.48 (m, 2H), 7.11–7.04 (m, 2H),
4.49 (t, J = 7.6 Hz, 2H), 4.05 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3): δ = 160.7 (d, J = 250.0 Hz), 155.5, 134.5 (d, J = 2.0 Hz), 120.2 (d,
J = 8.0 Hz), 116.0 (d, J = 23.0 Hz), 61.4, 45.6. IR (KBr): ν = 1738 cm-1
(C=O).
3-(o-tolyl)oxazolidin-2-one (9):[61] White oil. 1H NMR (400 MHz, CDCl3): δ
= 7.27–7.25 (m, 2H), 7.02–6.99 (m, 2H), 6.67–6.65 (m, 2H), 4.44 (t, J =
7.6 Hz, 2H), 4.01 (t, J = 8.4 Hz, 2H), 3.79 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ = 156.7, 136.0, 135.8, 131.2, 128.0, 126.9, 126.3, 62.3, 47.7,
17.7. IR (KBr): ν = 1743 cm-1 (C=O).
3-(3-chlorophenyl)oxazolidin-2-one (19):[62] White solid, m.p. 53.0–54.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.58 (t, J = 6.0 Hz, 1H), 7.46–7.44 (m,
1H), 7.30 (t, J = 8.0 Hz, 1H), 7.13–7.10 (m, 1H), 4.49 (t, J = 8.0 Hz, 2H),
4.04 (t, J = 8.4 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 155.1, 139.5,
135.0, 130.3, 124.2, 118.3, 116.2, 61.4, 45.2. IR (KBr): ν = 1736 cm-1
(C=O).
3-(m-tolyl)oxazolidin-2-one (10):[62] White solid, m.p. 84.0–86.0 oC. 1H
NMR (400 MHz, CDCl3): δ = 7.38 (s, 1H), 7.31–7.23 (m, 2H), 6.95 (d, J =
7.2 Hz, 1H), 4.45 (t, J = 7.6 Hz, 2H), 4.03 (t, J = 8.4 Hz, 2H), 2.37 (s, 3H).
13C NMR (100 MHz, CDCl3): δ = 155.4, 139.1, 138.3, 128.9, 125.0, 118.1,
115.5, 61.4, 45.4, 21.7. IR (KBr): ν = 1732 cm-1 (C=O).
3-(4-chlorophenyl)oxazolidin-2-one (20):[41] White solid, m.p. 118.5–119.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.51–7.47 (m, 2H), 7.35–7.32 (m, 2H),
4.49 (t, J = 8.0 Hz, 2H), 4.05 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3): δ = 155.2, 137.0, 129.4, 129.2, 118.5, 61.4, 45.3. IR (KBr): ν =
1747 cm-1 (C=O).
3-(p-tolyl)oxazolidin-2-one (11):[41] White solid, m.p. 90.0–91.0 oC. 1H
NMR (400 MHz, CDCl3): δ = 7.41 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 8.0 Hz,
2H), 4.46 (t, J = 8.0 Hz, 2H), 4.03 (t, J = 8.0 Hz, 2H), 2.33 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ = 155.5, 135.9, 133.9, 129.7, 118.5, 61.4,
45.9, 20.9. IR (KBr): ν = 1736 cm-1 (C=O).
3-(3-bromophenyl)oxazolidin-2-one (21):[65] White solid, m.p. 86.0–87.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.71 (s, 1H), 7.54–7.51 (m, 1H),
7.28–7.22 (m, 2H), 4.50 (t, J = 7.2 Hz, 2H), 4.04 (t, J = 8.4 Hz, 2H). 13C
NMR (100 MHz, CDCl3): δ = 155.0, 139.7, 130.5, 127.2, 123.0, 121.1,
116.7, 61.4, 45.2. IR (KBr): ν = 1728 cm-1 (C=O).
3-(2-methoxyphenyl)oxazolidin-2-one (12):[62] White solid, m.p. 62.0–63.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.36 (dd, J = 7.6 Hz, J = 1.6 Hz, 1H),
7.31–7.26 (m, 1H), 7.01–6.95 (m, 2H), 4.43 (t, J = 8.0 Hz, 2H), 3.98 (t, J
= 8.4 Hz, 2H), 3.86 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 157.6, 155.0,
129.0, 128.5, 126.1, 121.1, 112.1, 62.6, 55.8, 47.1. IR (KBr): ν = 1748
cm-1 (C=O).
3-(4-bromophenyl)oxazolidin-2-one (22):[41] White solid, m.p. 132.0–
133.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.50–7.43 (m, 4H), 4.50 (t, J =
8.0 Hz, 2H), 4.04 (t, J = 8.4 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ =
155.2, 137.5, 132.2, 118.3, 117.0, 61.4, 45.2. IR (KBr): ν = 1735 cm-1
(C=O).
3-(3-methoxyphenyl)oxazolidin-2-one (13):[61] White solid, m.p. 74.0–76.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.29–7.25 (m, 2H), 7.05–7.03 (m, 1H),
6.71–6.68 (m, 1H), 4.48 (t, J = 7.2 Hz, 2H), 4.05 (t, J = 8.0 Hz, 2H), 3.83
(s, 3H). 13C NMR (100 MHz, CDCl3): δ = 160.4, 155.3, 139.6, 129.9,
110.5, 109.8, 104.6, 61.4, 55.5, 45.5. IR (KBr): ν = 1749 cm-1 (C=O).
3-(naphthalen-1-yl)oxazolidin-2-one (23):[41] Gray solid; m.p. 129.5–130
oC. 1H NMR (400 MHz, CDCl3): δ = 7.92–7.85 (m, 3H), 7.59–7.47 (m, 4H),
4.63(t, J = 7.6 Hz, 2H), 4.09 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3): δ = 157.6, 134.7, 134.1, 130.0, 128.8, 128.7, 126.6, 125.7, 124.7,
122.4, 62.6, 48.2. IR (KBr): ν = 1741 cm-1 (C=O).
3-(4-methoxyphenyl)oxazolidin-2-one (14):[41] White solid, m.p. 109.0–
o
1
111.0 C. H NMR (400 MHz, CDCl3): δ = 7.46–7.42 (m, 2H), 6.93–6.89
(m, 2H), 4.47 (t, J = 8.0 Hz, 2H), 4.03 (t, J = 8.4 Hz, 2H), 3.80 (s, 3H). 13
C
3-(naphthalen-2-yl)oxazolidin-2-one (24):[60] Gray solid; m.p. 210.0–211.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.97–7.71 (m, 5H), 7.50–7.41 (m, 2H),
4.52 (t, J = 8.0 Hz, 2H), 4.16 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3): δ = 155.5, 136.1, 133.6, 130.4, 129.1, 127.7, 127.6, 126.8, 125.4,
118.4, 115.0, 61.6, 45.6. IR (KBr): ν = 1748 cm-1 (C=O).
NMR (100 MHz, CDCl3): δ = 156.5, 155.7, 131.5, 120.4, 114.4, 61.4,
55.6, 45.9. IR (KBr): ν = 1755 cm-1 (C=O).
3-(3-nitrophenyl)oxazolidin-2-one (15):[64] White solid, m.p. 110.0–112.0
oC. 1H NMR (400 MHz, CDCl3): δ = 8.25 (t, J = 2.0 Hz, 1H), 8.11–8.08 (m,
1H), 7.99–7.96 (m, 1H), 7.55 (t, J = 8.8 Hz, 1H), 4.56 (t, J = 8.0 Hz, 2H),
4.15 (t, J = 8.4 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 155.0, 148.7,
139.5, 130.1, 123.9, 118.6, 112.4, 61.6, 45.1. IR (KBr): ν = 1744 cm-1
(C=O).
3-(2,6-dimethylphenyl)oxazolidin-2-one (25):[66] White solid, m.p. 136.5–
137.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.18–7.10 (m, 3H), 4.57 (t, J =
8.0 Hz, 2H), 3.85 (t, J = 8.0 Hz, 2H), 2.29 (s, 6H). 13C NMR (100 MHz,
CDCl3): δ = 156.8, 136.9, 134.2, 128.9, 128.8, 62.6, 46.3, 17.9. IR (KBr):
ν = 1734 cm-1 (C=O).
3-(4-nitrophenyl)oxazolidin-2-one (16):[60] White solid, m.p. 154.0–155.0
oC. 1H NMR (400 MHz, CDCl3): δ = 8.26–8.22 (m, 2H), 7.74–7.70 (m, 2H),
4.56 (d, J = 7.6 Hz, 2H), 4.14 (d, J = 8.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3): δ = 154.7, 143.9, 143.4, 125.1, 117.5, 61.5, 45.0. IR (KBr): ν =
1753 cm-1 (C=O).
3-(4-bromo-2,6-dimethylphenyl)oxazolidin-2-one (26): White solid, m.p.
160.0–164.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.27 (s, 2H), 4.56 (t, J =
8.0 Hz, 2H), 3.81 (t, J = 8.0 Hz, 2H), 2.26 (s, 6H). 13C NMR (100 MHz,
CDCl3): δ = 156.5, 139.1, 133.4, 131.8, 122.5, 62.6, 46.1, 17.8. HRMS
(ESI) m/z: calcd for C11H12BrNO2Na [M+Na]+: 291.9949; found: 291.9922.
IR (KBr): ν = 1736 cm-1 (C=O).
3-(3-fluorophenyl)oxazolidin-2-one (17):[61] White solid, m.p. 87.0–88.0 oC.
1H NMR (400 MHz, CDCl3): δ = 7.45–7.41 (m, 1H), 7.34–7.29 (m, 1H),
7.23–7.20 (m, 1H), 6.85–6.80 (m, 1H), 4.48 (t, J = 8.0 Hz, 2H), 4.03 (t, J
= 8.4 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 163.1 (d, J = 250.0 Hz),
155.0, 139.9 (d, J = 11.0 Hz), 130.3 (d, J = 9.0 Hz), 113.3 (d, J = 3.0 Hz),
3-(2,6-diethylphenyl)oxazolidin-2-one (27):[62] Yellow oil, 1H NMR (400
MHz, CDCl3): δ = 7.30–7.25 (m, 1H), 7.15 (d, J = 8.0 Hz, 2H), 4.51 (t, J =
8.0 Hz, 2H), 3.87 (t, J = 8.4 Hz, 2H), 2.68–2.51 (m, 4H), 1.27–1.22 (m,
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10.1002/cctc.201800142
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6H). 13C NMR (100 MHz, CDCl3): δ = 157.2, 142.5, 132.9, 129.0, 126.7,
62.4, 47.5, 24.0, 14.6. IR (KBr): ν = 1748 cm-1 (C=O).
2H), 4.09 (t, J = 8.4 Hz, 2H), 2.41 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
= 170.6, 158.0, 154.5, 94.5, 63.0, 43.5, 12.8. HRMS (ESI) m/z: calcd. for
[M+H]+ C7H9N2O3: 169.0613; found: 169.0613. IR (KBr): ν = 1749 cm-1
(C=O).
3-(2,6-diisopropylphenyl)oxazolidin-2-one (28):[44] White solid, m.p.
150.0–152.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.35 (t, J = 7.6 Hz, 1H),
7.21 (d, J = 7.2 Hz, 2H), 4.56 (t, J = 8.0 Hz, 2H), 3.83 (t, J = 8.0 Hz, 2H),
3.02–2.95 (m, 2H), 1.25 (t, J = 6.8 Hz, 12H). 13C NMR (100 MHz, CDCl3):
δ = 157.7, 147.6, 131.4, 129.6, 124.4, 62.3, 49.9, 28.9, 24.6, 24.3. IR
(KBr): ν = 1801 cm-1 (C=O).
3-(benzo[d]thiazol-2-yl)oxazolidin-2-one (36): White solid, m.p. 150.0–
o
1
152.5 C. H NMR (400 MHz, CDCl3): δ = 7.82–7.79 (m, 2H), 7.46–7.42
(m, 1H), 7.33–7.29 (m, 1H), 4.66 (t, J = 8.0 Hz, 2H), 4.44 (t, J = 8.0 Hz,
2H). 13C NMR (100 MHz, CDCl3): δ = 157.5, 154.7, 148.4, 132.9, 124.2,
121.5, 121.4, 63.5, 45.1. HRMS (ESI) m/z: calcd. for [M+H]+
C10H9N2O2S: 221.0385; found: 221.0434. IR (KBr): ν = 1757 cm-1 (C=O).
3-(1-phenyl-1H-pyrazol-5-yl)oxazolidin-2-one (29): White solid, m.p.
127.5–129.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 2.0 Hz, 1H),
7.53–7.45 (m, 4H), 7.42–7.40 (m, 1H), 6.42 (d, J = 2.0 Hz, 1H), 4.35 (t, J
= 8.0 Hz, 2H), 3.60 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ =
156.6, 149.6, 138.6, 136.1, 129.0, 128.3, 124.2, 103.0, 62.7, 47.3. HRMS
(ESI) m/z: calcd. for [M+H]+ C12H12N3O2: 230.0930; found: 230.0942. IR
(KBr): ν = 1746 cm-1 (C=O).
3-(4-(3-fluoromorpholino)phenyl)oxazolidin-2-one (37):[63] White solid,
1
m.p. 147.5–148.0 oC. H NMR (400 MHz, CDCl3): δ = 7.42 (dd, J = 14.4
Hz, J = 2.4 Hz, 1H), 7.10 (d, J = 5.6 Hz, 1H), 6.91 (t, J = 9.2 Hz, 1H),
4.45 (t, J = 7.6 Hz, 2H), 4.99 (t, J = 8.0 Hz, 2H), 3.85 (t, J = 5.2 Hz, 4H),
3.03 (t, J = 4.8 Hz, 4H). 13C NMR (100 MHz, CDCl3): δ = 156.7, 155.0 (d,
J = 70.0 Hz), 136.5 (d, J = 8.8 Hz), 133.6 (d, J = 10.5 Hz), 119.9 (d, J =
4.2 Hz), 114.4 (d, J = 3.3 Hz), 107.6 (d, J = 26.3 Hz), 67.2, 61.5, 51.3,
45.5. IR (KBr): ν = 1755 cm-1 (C=O).
3-(3-methyl-1-phenyl-1H-pyrazol-5-yl)oxazolidin-2-one (30): White solid,
m.p. 93.0–94.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.51–7.44 (m, 2H),
7.40–7.36 (m, 1H), 6.24 (s, 1H), 4.35 (t, J = 8.0 Hz, 2H), 3.58 (t, J = 8.0
Hz, 2H), 2.33 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 156.5, 149.6,
138.6, 136.1, 129.6, 128.3, 124.2, 103.2, 62.7, 47.3, 14.2. HRMS (ESI)
m/z: calcd. for [M+H]+ C13H14N3O2: 244.1086; found: 244.1093. IR (KBr):
ν = 1759 cm-1 (C=O).
5-methyl-3-phenyloxazolidin-2-one (38a):[60] White solid, m.p. 79.5–81.5
oC. 1H NMR (400 MHz, CDCl3): δ = 7.55–7.52 (m, 2H), 7.39–7.35 (m, 2H),
7.15–7.11 (m, 1H), 4.83–4.75 (m, 1H), 4.12 (t, J = 8.4 Hz, 1H), 3.63 (t, J
= 7.6 Hz, 1H), 1.54 (d, J = 6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ =
155.0, 138.5, 129.2, 124.1, 118.3, 69.7, 52.0, 20.9. IR (KBr): ν = 1748
cm-1 (C=O).
3-(3-methyl-1-(p-tolyl)-1H-pyrazol-5-yl)oxazolidin-2-one (31): White solid,
m.p. 109.0–110.5 oC. 1H NMR (400 MHz, CDCl3): δ = 7.34 (d, J = 8.0 Hz,
2H), 7.23 (d, J = 8.4 Hz, 2H), 6.21 (s, 1H), 4.33 (t, J = 7.6 Hz, 2H), 3.56 (t,
J = 8.0 Hz, 2H), 2.38 (s, 3H), 2.30 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
= 156.5, 149.2, 138.2, 136.1, 136.0, 130.0, 124.0, 103.0, 62.7, 47.1, 21.2,
14.2. HRMS (ESI) m/z: calcd. for [M+H]+ C14H16N3O2: 258.1243; found:
258.1243. IR (KBr): ν = 1743 cm-1 (C=O).
4-methyl-3-phenyloxazolidin-2-one (38b):[67] White oil. 1H NMR (400 MHz,
CDCl3): δ = 7.44–7.37 (m, 4H), 7.21–7.17 (m, 1H), 4.59–4.50 (m, 2H),
4.02 (dd, J = 8.0 Hz, J = 5.6 Hz, 1H), 1.33 (d, J = 5.6 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ = 155.9, 136.6, 129.3, 125.4, 122.1, 68.8, 52.5, 18.6.
IR (KBr): ν = 1752 cm-1 (C=O).
3-(1,3-diphenyl-1H-pyrazol-5-yl)oxazolidin-2-one (32): White solid, m.p.
5-methyl-3-(p-tolyl)oxazolidin-2-one (39a):[67] White solid, mp 65.0–66.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.41–7.39 (m, 2H), 7.17–7.15 (m, 2H),
4.81–4.72 (m, 1H), 4.08 (d, J = 8.0 Hz, 1H), 3.59 (t, J = 8.0 Hz, 1H), 3.32
(s, 3H), 1.52 (d, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 155.1,
136.0, 133.7, 129.7, 118.4, 69.6, 52.2, 20.9, 20.8. IR (KBr): ν = 1750 cm-1
(C=O).
o
1
91.0–92.5 C. H NMR (400 MHz, CDCl3): δ = 7.86–7.84 (m, 2H), 7.61–
7.58 (m, 2H), 7.51 (t, J = 7.2 Hz, 2H), 7.45–7.40 (m, 3H), 7.34 (t, J = 7.2
Hz, 1H), 6.77 (s, 1H), 4.40 (t, J = 7.6 Hz, 2H), 3.65 (t, J = 8.0 Hz, 2H). 13
C
NMR (100 MHz, CDCl3): δ = 156.5, 151.9, 138.7, 137.0, 132.8, 128.7,
128.6, 128.4, 125.8, 124.4, 101.0, 62.8, 47.4. HRMS (ESI) m/z: calcd. for
[M+H]+ C18H16N3O2: 306.1243; found: 306.1241. IR (KBr): ν = 1747 cm-1
(C=O).
4-methyl-3-(p-tolyl)oxazolidin-2-one (39b):[67] White oil. 1H NMR (400
MHz, CDCl3): δ = 7.29–7.26 (m, 2H), 7.19 (d, J = 8.4 Hz, 2H), 4.55 (t, J =
8.0 Hz, 1H), 4.50–4.42 (m, 1H), 4.00 (dd, J = 8.4 Hz, J = 6.0 Hz, 1H),
2.33 (s, 3H), 1.29 (d, J = 6.0 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ =
156.0, 135.3, 134.0, 129.8, 122.5, 68.8, 52.7, 21.0, 18.5. IR (KBr): ν =
1749 cm-1 (C=O).
3-(1-phenyl-3-(p-tolyl)-1H-pyrazol-5-yl)oxazolidin-2-one (33): White solid,
m.p. 97.0–98.5 oC. 1H NMR (400 MHz, CDCl3): δ = 7.80–7.76 (m, 2H),
7.61–7.58 (m, 2H), 7.52–7.49 (m, 2H), 7.44–7.40 (m, 1H), 6.96–6.94 (m,
2H), 6.70 (s, 1H), 4.38 (t, J = 8.0 Hz, 2H), 3.84 (s, 3H), 3.63 (t, J = 8.0 Hz,
2H). 13C NMR (100 MHz, CDCl3): δ = 159.9, 156.5, 151.8, 138.7, 136.8,
129.6, 128.5, 127.1, 125.6, 124.3, 114.2, 100.6, 62.8, 55.4, 47.4. HRMS
(ESI) m/z: calcd. for [M+H]+ C19H18N3O2: 320.1399; found: 320.1399. IR
(KBr): ν = 1756 cm-1 (C=O).
3-(4-methoxyphenyl)-5-methyloxazolidin-2-one (40a):[65] White solid, m.p.
88.0–89.0 oC.1H NMR (400 MHz, CDCl3): δ = 7.27 (s, 2H), 6.87–6.83 (m,
2H), 4.20 (dd, J = 7.2 Hz, J = 2.8 Hz, 1H), 4.10–3.98 (m, 1H), 3.78 (s,
3H), 3.75–3.62 (m, 1H), 1.29 (d, J = 6.0 Hz, 3H). 13C NMR (100 MHz,
CDCl3): δ = 156.4, 155.4, 129.4, 124.9, 114.6, 68.9, 55.6, 55.3, 20.8. IR
(KBr): ν = 1749 cm-1 (C=O).
3-(3-(4-methoxyphenyl)-1-phenyl-1H-pyrazol-5-yl)oxazolidin-2-one (34):
White solid, m.p. 97.5–99.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.79–
7.76 (m, 2H), 7.61–7.58 (m, 2H), 7.52–7.49 (m, 2H), 7.44–7.40 (m, 1H),
6.96–6.93 (m, 2H), 6.70 (s, 1H), 4.39 (t, J = 8.0 Hz, 2H), 3.85 (s, 3H),
3.64 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 159.9, 156.5,
151.8, 138.7, 136.8, 129.6, 128.5, 127.1, 125.6, 124.4, 114.2, 100.6,
62.8, 47.4. HRMS (ESI) m/z: calcd. for [M+H]+ C19H18N3O3: 336.1348;
found: 336.1358. IR (KBr): ν = 1747 cm-1 (C=O).
3-(4-methoxyphenyl)-4-methyloxazolidin-2-one (40b):[67] White oil. 1H
NMR (400 MHz, CDCl3): δ = 7.29–7.26 (m, 2H), 6.83–6.91 (m, 2H), 4.56
(t, J = 8.0 Hz, 1H), 4.42–4.37 (m, 1H), 3.99 (dd, J = 8.8 Hz, J = 7.6 Hz,
1H), 3.80 (s, 3H), 1.28 (d, J = 6.0 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ
= 157.7, 156.4, 129.4, 124.9, 114.6, 68.9, 55.6, 53.3, 18.6. IR (KBr): ν =
1755 cm-1 (C=O).
3-(5-methylisoxazol-3-yl)oxazolidin-2-one (35): White solid, m.p. 71.0–
73.0 oC. 1H NMR (400 MHz, CDCl3): δ = 6.68 (s, 1H), 4.55 (t, J = 7.6 Hz,
This article is protected by copyright. All rights reserved.

10.1002/cctc.201800142
ChemCatChem
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3-(4-iodophenyl)-5-methyloxazolidin-2-one (41a):[68] White oil. 1H NMR
(400 MHz, CDCl3): δ = 7.67–7.63 (m, 2H), 7.33–7.29 (m, 2H), 4.83–4.74
(m, 1H), 4.07 (t, J = 8.4 Hz, 1H), 3.57 (dd, J = 8.8 Hz, J = 7.2 Hz, 1H),
1.53 (d, J = 6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 154.7, 138.3,
138.0, 120.0, 87.4, 69.7, 51.7, 20.8. IR (KBr): ν = 1750 cm-1 (C=O).
3-(4-nitrophenyl)-1,3-oxazinan-2-one (48):[69] White solid, m.p. 125.0–
o
1
126.0 C. H NMR (400 MHz, CDCl3): δ = 8.27–8.23 (m, 2H), 7.58–7.55
(m, 2H), 4.47 (t, J = 6.4 Hz, 2H), 3.83 (t, J = 6.0 Hz, 2H), 2.30–2.25 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 152.0, 148.6, 145.2, 125.2, 124.6,
67.4, 48.1, 22.5. IR (KBr): ν = 1679 cm-1 (C=O).
3-(4-iodophenyl)-4-methyloxazolidin-2-one (41b):[68] White oil. 1H NMR
(400 MHz, CDCl3): δ = 7.70–7.66 (m, 2H), 7.22–7.18 (m, 2H), 4.56 (t, J =
8.0 Hz, 1H), 4.53–4.45 (m, 1H), 4.01 (dd, J = 8.0 Hz, J = 5.2 Hz, 1H),
1.32 (d, J = 6.0 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 155.4, 138.2,
136.6, 123.4, 89.0, 68.7, 52.1, 18.4. IR (KBr): ν = 1749 cm-1 (C=O).
3-(4-iodophenyl)-1,3-oxazinan-2-one (49):[44] White solid, m.p. 72.0–73.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.71–7.68 (m, 2H), 7.11–7.08 (m, 2H),
4.42 (t, J = 5.6 Hz, 2H), 3.70 (t, J = 6.0 Hz, 2H), 2.22–2.17 (m, 2H). 13C
NMR (100 MHz, CDCl3): δ = 152.5, 148.4, 138.4, 127.8, 91.6, 67.2, 48.7,
22.6. IR (KBr): ν = 1690 cm-1 (C=O).
3-(3-chlorophenyl)-5-methyloxazolidin-2-one (42a):[41] White oil. 1H NMR
(400 MHz, CDCl3): δ = 7.56 (t, J = 2.0 Hz, 1H), 7.47–7.44 (m, 1H), 7.29 (t,
J = 8.0 Hz, 1H), 7.12–7.09 (m, 1H), 4.83–4.78 (m, 1H), 4.10 (t, J = 4.4 Hz,
1H), 3.61 (t, J = 7.2 Hz, 1H), 1.54 (t, J = 6.0 Hz, 3H). 13C NMR (100 MHz,
CDCl3): δ = 154.7, 139.7, 135.0, 130.2, 124.1, 118.3, 116.2, 69.8, 51.9,
20.8. IR (KBr): ν = 1749 cm-1 (C=O).
3-(4-(trifluoromethyl)phenyl)-1,3-oxazinan-2-one (50):[44] White solid, m.p.
o
76.0–78.0 C. 1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 8.4 Hz, 2H),
7.48 (d, J = 8.4 Hz, 2H), 4.45 (t, J = 6.4 Hz, 2H), 3.77 (t, J = 6.0 Hz, 2H),
2.27–2.21 (m, 2H). 13C NMR (100 MHz, CDCl3): δ = 152.4, 146.1, 128.8
(q, J = 32.5 Hz), 126.4 (q, J = 3.8 Hz), 125.7, 122.6, 100.1, 67.3, 48.5,
22.6. IR (KBr): ν = 1697 cm-1 (C=O).
3-(3-chlorophenyl)-4-methyloxazolidin-2-one (42b):[67] White oil. 1H NMR
(400 MHz, CDCl3): δ = 7.49 (t, J = 2.0 Hz, 1H), 7.37–7.28 (m, 2H), 7.17–
7.15 (m, 1H), 4.58 (t, J = 8.0 Hz, 1H), 4.55–4.48 (m, 1H), 4.04 (dd, J =
8.0 Hz, J = 5.2 Hz, 1H), 1.36 (t, J = 6.0 Hz, 3H). 13C NMR (100 MHz,
CDCl3): δ = 155.4, 138.0, 135.1, 130.3, 125.2, 121.6, 118.5, 68.8, 52.3,
18.6. IR (KBr): ν = 1748 cm-1 (C=O).
4-(2-oxo-1,3-oxazinan-3-yl)benzonitrile (51):[71] White solid, m.p. 123.0–
o
1
125.0 C. H NMR (400 MHz, CDCl3): δ = 7.69–7.65 (m, 2H), 7.52–7.49
(m, 2H), 4.45 (t, J = 5.6 Hz, 2H), 3.78 (t, J = 6.0 Hz, 2H), 2.28–2.22 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 152.1, 147.0, 133.1, 125.6, 118.5,
109.8, 67.3, 48.1, 22.6. IR (KBr): ν = 1694 cm-1 (C=O).
3-(4-fluorophenyl)-1,3-oxazinan-2-one (52):[44] White solid, m.p. 88.0–
89.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.30–7.25 (m, 2H), 7.09–7.03
(m, 2H), 4.40 (t, J = 5.2 Hz, 2H), 3.67 (t, J = 6.4 Hz, 2H), 2.22–2.16 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 161.0 (d, J = 247.0 Hz), 159.9,
153.0, 139.0, 127.6 (d, J = 8.5 Hz), 115.9 (d, J = 22.7 Hz), 67.1, 49.1,
22.6. IR (KBr): ν = 1694 cm-1 (C=O).
3-(4-iodophenyl)-4,5-dimethyloxazolidin-2-one (43): White oil. 1H NMR
(400 MHz, CDCl3): δ = 7.69–7.66 (m, 2H), 7.28–7.26 (m, 2H), 4.83–4.78
(m, 1H), 4.43–4.39 (m, 1H), 1.42 (d, J = 6.8 Hz, 3H), 1.20 (d, J = 6.4 Hz,
3H). 13C NMR (100 MHz, CDCl3): δ = 155.0, 138.3, 137.1, 123.0, 88.6,
73.5, 55.7, 29.8, 14.8. HRMS (ESI) m/z: calcd. for [M+H]+ C11H12INO2:
317.9991; found: 317.9994. IR (KBr): ν = 1733 cm-1 (C=O).
3-(m-tolyl)-1,3-oxazinan-2-one (53): White oil. 1H NMR (400 MHz,
CDCl3): δ = 7.26 (t, J = 8.0 Hz, 1H), 7.13–7.06 (m, 3H), 4.39 (t, J = 6.0
Hz, 2H), 3.68 (t, J = 6.0 Hz, 2H), 2.34 (s, 3H), 2.21–2.15 (m, 2H). 13C
NMR (100 MHz, CDCl3): δ = 153.8, 142.9, 139.2, 129.1, 127.8, 126.8,
123.0, 67.0, 48.0, 22.6, 21.4. HRMS (ESI) m/z: calcd. for [M+H]+
C11H14NO2: 192.1025; found: 192.0999. IR (KBr): ν = 1698 cm-1 (C=O).
3-(4-butylphenyl)-4,5-dimethyloxazolidin-2-one (44): Yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 7.36–7.32 (m, 2H), 7.20–7.17 (m, 2H), 4.84–4.77
(m, 1H), 4.43–4.36 (m, 1H), 2.59 (t, J = 3.6 Hz, 2H), 1.62–1.54 (m, 2H),
1.41 (d, J = 6.4 Hz, 3H), 1.38–1.36 (m, 2H), 1.17 (d, J = 6.4 Hz, 3H), 0.92
(t, J = 7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 155.6, 140.1, 134.6,
129.2, 122.2, 73.4, 56.2, 35.2, 33.7, 29.8, 22.4, 14.9, 14.1. HRMS (ESI)
m/z: calcd. for [M+H]+ C15H21INO2: 248.1651; found: 248.1671. IR (KBr):
ν = 1749 cm-1 (C=O).
3-(p-tolyl)-1,3-oxazinan-2-one (54):[71] White solid, m.p. 127.0–128.0 oC.
1H NMR (400 MHz, CDCl3): δ = 7.19 (s, 4H), 4.41 (t, J = 5.2 Hz, 2H),
3.69 (t, J = 1.2 Hz, 2H), 2.34 (s, 3H), 2.22–2.16 (m, 2H). 13C NMR (100
MHz, CDCl3): δ = 153.1, 140.5, 136.9, 130.0, 125.9, 67.1, 48.1, 22.7,
21.2. IR (KBr): ν = 1744 cm-1 (C=O).
3-phenyl-1,3-oxazinan-2-one (45):[71] White solid, m.p. 97.0–98.0 oC. 1H
NMR (400 MHz, CDCl3): δ = 7.40–7.36 (m, 2H), 7.32–7.30 (m, 2H),
7.17–7.13 (m, 1H), 4.40 (t, J = 8.0 Hz, 2H), 3.70 (t, J = 8.0 Hz, 2H), 2.21–
2.16 (m, 2H). 13C NMR (100 MHz, CDCl3): δ = 152.9, 143.0, 129.3, 127.0,
126.0, 67.1, 48.9, 22.6. IR (KBr): ν = 1745 cm-1 (C=O).
3-(3-methoxyphenyl)-1,3-oxazinan-2-one (55): White oil. 1H NMR (400
MHz, CDCl3): δ = 7.23 (t, J = 7.6 Hz, 1H), 7.10–7.03 (m, 2H), 6.85–6.76
(m, 1H), 4.34 (t, J = 5.6 Hz, 2H), 3.63 (t, J = 6.8 Hz, 2H), 2.32 (s, 3H),
2.16–2.10 (m, 2H). 13C NMR (100 MHz, CDCl3): δ = 160.0, 152.8, 142.8,
138.9, 128.8, 126.5, 122.8, 66.9, 55.2, 48.7, 22.3. HRMS (ESI) m/z:
calcd. for [M+H]+ C11H14NO3: 208.0974; found: 208.0943. IR (KBr): ν =
1698 cm-1 (C=O).
3-(4-ethylphenyl)-1,3-oxazinan-2-one (46): White solid, m.p. 88.0–89.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.21 (s, 4H), 4.39 (t, J = 5.6 Hz, 2H),
3.68 (t, J = 6.4 Hz, 2H), 2.63 (q, J = 8.0 Hz, 2H), 2.18–2.16 (m, 2H), 1.22
(t, J = 7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 153.0, 143.0, 140.6,
128.7, 125.8, 67.0, 48.0, 28.5, 22.6, 15.5. HRMS (ESI) m/z: calcd. for
[M+H]+ C12H16NO2: 206.1181; found: 206.1156. IR (KBr): ν = 1694 cm-1
(C=O).
3-(4-methoxyphenyl)-1,3-oxazinan-2-one (56):[71] White solid, m.p.
101.0–102.5 oC. 1H NMR (400 MHz, CDCl3): δ = 7.23–7.19 (m, 2H),
6.92–6.88 (m, 2H), 4.39 (t, J = 5.2 Hz, 2H), 3.79 (s, 3H), 3.66 (t, J = 6.0
Hz, 2H), 2.20–2.14 (m, 2H). 13C NMR (100 MHz, CDCl3): δ = 158.3,
153.3, 136.0, 127.4, 114.6, 67.0, 55.6, 49.3, 22.7. IR (KBr): ν = 1694 cm-1
(C=O).
3-(4-butylphenyl)-1,3-oxazinan-2-one (47): White solid, m.p. 92.0–93.0
oC. 1H NMR (400 MHz, CDCl3): δ = 7.22–7.17 (m, 4H), 4.39 (t, J = 5.2 Hz,
2H), 3.68 (t, J = 6.0 Hz, 2H), 2.60 (t, J = 8.0 Hz, 2H), 2.20–2.14 (m, 2H),
1.62–1.54 (m, 2H), 1.39–1.30 (m, 2H), 0.91 (t, J = 7.2 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ = 153.0, 141.7, 140.6, 129.3, 125.7, 67.0, 48.0, 35.3,
33.6, 22.7, 22.4, 14.0. HRMS (ESI) m/z: calcd. for [M+H]+ C14H20NO2:
234.1494; found: 234.1488. IR (KBr): ν = 1695 cm-1 (C=O).
3-(3-chlorophenyl)-1,3-oxazinan-2-one (57): White oil. 1H NMR (400 MHz,
CDCl3): δ = 7. 34 (t, J = 2.0 Hz, 1H), 7.33–7.28 (m, 2H), 7.25–7.21 (m,
1H), 4.40 (t, J = 6.0 Hz, 2H), 3.70 (t, J = 5.6 Hz, 2H), 2.22–2.16 (m, 2H).
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10.1002/cctc.201800142
ChemCatChem
FULL PAPER
13C NMR (100 MHz, CDCl3): δ = 152.5, 144.4, 134.6, 130.2, 127.0, 126.2,
124.1, 67.2, 48.7, 22.6. HRMS (ESI) m/z: calcd. for [M+H]+ C10H11ClNO2:
212.0478; found: 212.0459. IR (KBr): ν = 1701 cm-1 (C=O).
29.1, 28.5, 27.0, 15.6. HRMS (ESI) m/z: calcd. for [M+H]+ C13H17NO2:
220.1338; found: 220.1341. IR (KBr): ν = 1792 cm-1 (C=O).
5-chloropentyl phenylcarbamate (67):[44] Yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 7.39 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 8.0 Hz, 2H), 7.06 (t, J =
3.6 Hz, 1H), 6.76 (s, 1H), 4.17 (t, J = 10.4 Hz, 2H), 3.54 (t, J = 6.8 Hz,
2H), 1.85–1.76 (m, 2H), 1.74–1.67 (m, 2H), 1.58–1.51 (m, 3H). 13C NMR
(100 MHz, CDCl3): δ = 153.7, 138.0, 129.1, 123.5, 118.8, 65.0, 44.9, 32.2,
28.3, 23.4. IR (KBr): ν = 1744 cm-1 (C=O).
3-(4-chlorophenyl)-1,3-oxazinan-2-one (58):[71] White solid, m.p. 88.0–
89.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.35–7.32 (m, 2H), 7.28–7.24
(m, 2H), 4.40 (t, J = 6.0 Hz, 2H), 3.69 (t, J = 6.4 Hz, 2H), 2.22–2.16 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 158.3, 153.3, 136.0, 127.4, 114.6,
67.0, 55.6, 49.3, 22.7. IR (KBr): ν = 1687 cm-1 (C=O).
3-(3-bromophenyl)-1,3-oxazinan-2-one (59):[44] White oil. 1H NMR (400
MHz, CDCl3): δ = 7. 53 (t, J = 2.0 Hz, 1H), 7.43–7.40 (m, 1H), 7.33–7.26
(m, 1H), 4.44 (t, J = 5.2 Hz, 2H), 3.73 (t, J = 6.4 Hz, 2H), 2.26–2.20 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 152.9, 144.3, 130.5, 130.0, 129.1,
124.7, 122.5, 67.2, 48.8, 22.6. IR (KBr): ν = 1663 cm-1 (C=O).
6-chlorohexyl phenylcarbamate (68):[70] Yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 7.39–7.34 (m, 4H), 7.32–7.28 (m, 1H), 7.06 (s, 1H), 4.17 (t, J
= 6.8 Hz, 2H), 3.54 (t, J = 6.8 Hz, 2H), 1.83–1.76 (m, 2H), 1.74–1.66 (m,
2H), 1.52–1.40 (m, 4H). 13C NMR (100 MHz, CDCl3): δ = 153.8, 138.0,
129.2, 129.0, 123.5, 118.8, 65.3, 45.1, 32.6, 28.9, 26.7, 25.4. IR (KBr): ν
= 1701 cm-1 (C=O).
3-(4-bromophenyl)-1,3-oxazinan-2-one (60):[71] White solid, m.p. 81.0–
83.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.72–7.68 (m, 2H), 7.11–7.09
(m, 1H), 4.42 (t, J = 5.6 Hz, 2H), 3.70 (t, J = 6.0 Hz, 2H), 2.23–2.18 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 152.6, 142.1, 132.4, 127.6, 120.4,
67.2, 48.8, 22.6. IR (KBr): ν = 1695 cm-1 (C=O).
10-chlorodecyl phenylcarbamate (69):[72] Yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 7.36 (d, J = 12.0 Hz, 2H), 7.30 (t, J = 7.2 Hz, 2H), 7.05 (t, J =
7.2Hz, 1H), 6.61 (s, 1H), 4.15 (t, J = 6.8 Hz, 2H), 3.53 (t, J = 6.8 Hz, 4H),
1.80–1.73 (m, 4H), 1.68–1.62 (m, 5H), 1.42–1.37 (m, 5H). 13C NMR (100
MHz, CDCl3): δ = 155.6, 138.1, 129.1, 123.4, 118.7, 68.1, 65.5, 45.3,
32.7, 29.5, 29.3, 29.1, 29.0, 27.0, 26.0. IR (KBr): ν = 1739 cm-1 (C=O).
3-(naphthalen-1-yl)-1,3-oxazinan-2-one (61):[71] White solid, m.p. 120.0–
o
1
121.0 C. H NMR (400 MHz, CDCl3): δ = 7.91–7.81 (m, 3H), 7.57–7.43
(m, 4H), 4.59–4.49 (m, 2H), 3.77–3.65 (m, 2H), 2.39–2.20 (m, 2H). 13C
NMR (100 MHz, CDCl3): δ = 153.1, 140.7, 133.7, 132.1, 129.2, 127.8,
126.6, 124.8, 123.7, 99.8, 67.2, 48.1, 22.8. IR (KBr): ν = 1701 cm-1 (C=O).
Acknowledgements
We are grateful to 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 financial support.
3-(naphthalen-2-yl)-1,3-oxazinan-2-one (62): White solid, m.p. 115.0–
o
1
117.0 C. H NMR (400 MHz, CDCl3): δ = 7.87–7.75 (m, 4H), 7.50–7.47
(m, 3H), 4.47 (t, J = 5.2 Hz, 2H), 3.84 (t, J = 6.4 Hz, 2H), 2.29–2.23 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 153.1, 139.2, 134.8, 129.5, 128.8,
128.6, 127.2, 126.5, 125.9, 125.4, 122.0, 67.3, 48.7, 27.8. HRMS (ESI)
m/z: calcd. for [M+H]+ C14H14NO2: 228.1025; found: 228.1028. IR (KBr): ν
= 1697 cm-1 (C=O).
Keywords: carbon dioxide • 3-component reaction • NHC •
3-(2,6-diisopropylphenyl)-1,3-oxazinan-2-one (63):[44] White solid, m.p.
145.0–147.0 oC. 1H NMR (400 MHz, CDCl3): δ = 7.32 (t, J = 8.0 Hz, 1H),
7.20 (t, J = 3.6 Hz, 2H), 4.46 (t, J = 5.2 Hz, 2H), 3.46 (t, J = 5.6 Hz, 2H),
3.00–2.95 (m, 2H), 2.24–2.18 (m, 2H), 1.25 (dd, J = 10.4 Hz, J = 7.2 Hz,
12H). 13C NMR (100 MHz, CDCl3): δ = 152.9, 145.9, 137.1, 128.9, 124.4,
67.1, 48.5, 28.7, 24.5, 24.4, 22.5. IR (KBr): ν = 1690 cm-1 (C=O).
oxazolidinones
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Entry for the Table of Contents
FULL PAPER
Congmin Mei, Yibo Zhao, Qianwei
Chen, Changsheng Cao,* Guangsheng
Pang, Yanhui Shi*
Page No. – Page No.
Synthesis of oxazolidinones and
derivatives through three-component
fixation of carbon dioxide
An effective and recyclable catalytic system for the synthesis of N-Aryl-2-
oxazolidinones through CO2 with ready available dichloroalkanes and aromatic
amines under mild conditiones has been invented. Different ring member of
oxazolidinones can be synthesised through this method. Few water and air of CO2
have little effect on the catalytic system. The catalyst can be reused at least 3 times
without obvious loss of catalytic activity.
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