Facile and mild process for chemical fixation of CO2 to 4-methylene-1,3-oxazolidin-2-ones under solvent-free conditions

Article abstract of DOI:10.1080/00397911003707014

4-Methylene-1,3-oxazolidin-2-ones were prepared via the cycloadditon reaction of propargylic alcohols with primary amines and CO₂ under atmospheric pressure at 60°C in the absence of any additional solvent. This methodology affords an ecofriend

Full text of DOI:10.1080/00397911003707014

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Facile and Mild Process for Chemical
Fixation of CO to 4-Methylene-1,3-
2
oxazolidin-2-ones Under Solvent-Free
Conditions
a
a
a
a
Jingxiu Xu , Jinwu Zhao , Zhenbin Jia & Jianhe Zhang
a
School of Pharmacy, Guangdong Medical College, Dongguan, China
Published online: 25 Feb 2011.
To cite this article: Jingxiu Xu , Jinwu Zhao , Zhenbin Jia & Jianhe Zhang (2011): Facile and Mild
Process for Chemical Fixation of CO to 4-Methylene-1,3-oxazolidin-2-ones Under Solvent-Free
2
Conditions, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 41:6, 858-863
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1
Synthetic Communications , 41: 858–863, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911003707014
FACILE AND MILD PROCESS FOR CHEMICAL FIXATION
OF CO TO 4-METHYLENE-1,3-OXAZOLIDIN-2-ONES
2
UNDER SOLVENT-FREE CONDITIONS
Jingxiu Xu, Jinwu Zhao, Zhenbin Jia, and Jianhe Zhang
School of Pharmacy, Guangdong Medical College, Dongguan, China
GRAPHICAL ABSTRACT
Abstract 4-Methylene-1,3-oxazolidin-2-ones were prepared via the cycloadditon reaction of
ꢀ
propargylic alcohols with primary amines and CO under atmospheric pressure at 60 C in
the absence of any additional solvent. This methodology affords an ecofriendly, mild, and
easy approach to chemical fixation of CO
2
2
.
Keywords Carbon dioxide; chemical fixation; oxazolidinone; propargylic alcohol;
solvent-free
Carbon dioxide (CO ) is a major greenhouse gas, and a great deal of CO is con-
2
2
stantly emitted into the atmosphere from burning fossil fuels. The issue of recycling
or removing CO from industrial emissions is receiving increased attention. How-
2
ever, CO is both an abundant and cheap nontoxic biorenewable resource. It is an
2
attractive raw material for use in important industrial processes to replace toxic
chemicals such as phosgene, isocyanates, or CO. Hence, chemical fixation of CO
2
[
1]
into useful compounds attracts growing concern.
,3-Oxazolidin-2-ones constitute a very important class of heterocyclic com-
pounds. They can be employed as multipurpose chiral synthons in asymmetric synth-
1
[
2]
eses of biologically active compounds or their synthetic intermediates. Chiral
,3-oxazolidin-2-ones are widely used as chiral auxiliaries in many important
1
[3]
asymmetric syntheses. Moreover, some oxazolidinones such as DUP-105, DUP-
21, and linezolid (Zyvox) have attracted interest as monodrug- or multidrug-
7
[4]
resistant antibacterial agents. The importance of these heterocyclic derivatives
justifies the continuous efforts to develop novel approaches to their synthesis. A
[
5]
number of procedures to synthesize 2-oxazolidinones have been developed.
Received September 15, 2008.
Address correspondence to Jinwu Zhao, School of Pharmacy, Guangdong Medical College,
Xincheng Avenue, Songshan Lake Science and Industrial Park, Dongguan, China. E-mail:
jinwuzhao@gmail.com
1
8
58

CHEMICAL FIXATION OF CO
2
859
Scheme 1. Cycloaddition reaction of propargylic alcohols with amines in a CO
solvent-free conditions.
2
atmosphere under
4
-Methylene-1,3-oxazolidin-2-ones can be further transformed into synthetically
useful derivatives because they bear an exocyclic double bond. It was reported that
-methylene-1,3-oxazolidin-2-ones can be prepared via the cycloaddition of pro-
4
[
6]
pargylic alcohols with primary amines and CO2. However, these reported proto-
cols have suffered from drawbacks such as high temperature and high CO2
pressure. Recently, we found that 4-methylene-1,3-oxazolidin-2-ones could be
synthesized via the cycloaddition reaction of propargylic alcohols with primary
amine in a CO atmosphere under solvent-free conditions (Scheme 1).
2
We initially examined the reaction of 2-methylbut-3-yn-2-ol (1a) and n-butyla-
mine (2a) in a CO atmosphere to optimize the reaction condition, and the results are
2
summarized in Table 1. A series of metal salts was screened to drive the cycloadditon
ꢀ
reaction at 60 C for 24 h in which the ratio of propargylic alcohol to primary amine
was 1:2. As can be seen from Table 1, cuprous salts could catalyze the reaction, and
cuprous chloride was better then cuprous iodide and cuprous bromide (entries 1–3).
Only trace amounts of 3-butyl-5,5-dimethyl-4-methyleneoxazolidin-2-one were
Table 1. Optimizing reaction conditions for cycloaddition of propargylic alcohols with amines in a CO
a
atmosphere
2
ꢀ
b
Yield (%)
Entry
Temperature ( C)
Alcohol=amine
Catalyst
1
2
3
4
5
6
7
8
9
60
60
60
60
60
60
60
80
40
1:2
1:2
1:2
1:2
1:2
1:1
1:3
1:2
1:2
CuI
CuBr
CuCl
72
75
81
Trace
FeCl
ZnCl
2
c
0
2
CuCl
CuCl
CuCl
CuCl
68
81
80
55
a
Condition: 2-methylbut-3-yn-2-ol (2 mmol), n-butylamine (2–6 mmol), catalyst (0.1 mmol).
b
Isolated yields based on 2-methylbut-3-yn-2-ol.
c
2
-Methylbut-3-yn-2-ol remained unchanged.

860
J. XU ET AL.
obtained with the catalysis of ferrous chloride, and zinc chloride could not promote
the reaction at all (entries 4 and 5). When the ratio of alcohol to amine was regulated
to 1:1, the yield decreased to 68% (entry 6), and raising the quantity of amine could
not further improve the cycloaddition reaction (entry 7). When the reaction was car-
ꢀ
ried out at 80 C (entry 8), the isolated yield was unchanged, while the yield was only
ꢀ
5
2
5% at 40 C (entry 9). Therefore, the best reaction conditions were as follows:
-methylbut-3-yn-2-ol (1a; 2 mmol), n-butylamine (2a; 4 mmol), cuprous chloride
ꢀ
(0.1 mmol) as catalyst, a temperature of 60 C, and a reaction time of 24 h.
We then explored the generality and scope of the reaction (Table 2). A variety
of primary amines were employed to react with 2-methylbut-3-yn-2-ol (1a) in an
atmosphere of CO under the optimal reaction conditions. As the results showed,
2
the steric hindrance of the substituents on the primary amines could affect the
cycloaddition significantly. Thus, when n-, sec-, and tert-butylamine were employed,
n-butylamine (2a) yielded the best result (81% isolated yield; entry 1), but no desired
product was detected when tert-butylamine was used (entry 3). Allylamine (2c) and
cyclohexylamine (2d) could also proceed efficiently with yields of 77% and 83%
respectively (entries 4 and 5). However, aniline could not react at all, and 1a was
recovered (entry 6). Various propargylic alcohols, such as 1-ethynylcyclohexanol
(
1b), 2-phenylbut-3-yn-2-ol (1c), 3,4-dimethylpent-1-yn-3-ol (1d), and 3-methylnon-
-yn-3-ol (1e) successfully unterwent cycyloaddition with n-butylamine (2a) in the
atmosphere of CO under the given conditions. The corresponding 4-methylene-1,3-
1
2
oxazolidin-2-ones 3e–h could be obtained in 63–84% yields (entries 7–10). However,
Table 2. Synthesis of 4-methylene-2-oxazolidinones from corresponding propargylic alcohols and
a
primary amines in a CO atmosphere
2
1
R
2
R
3
R
b
Yield (%)
Entry
Product
1
2
3
4
5
6
7
8
9
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
n-Bu
s-Bu
t-Bu
Allyl
Cy
3a
3b
81
70
c
NO
3c
0
77
83
3d
d
0
Ph
NO
3e
-C
5
H
10
-
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
84
87
69
63
Me
Me
Me
H
Ph
i-Pr
3f
3g
1
1
1
0
1
2
n-C
5
H
13
3h
d
Me
H
NO
NO
0
d
0
H
a
b
c
ꢀ
Reagents and conditions: alcohol 1 (2 mmol), amine 2 (4 mmol), CuCl (0.1 mmol), 60 C, 24 h.
Isolated yield based on alcohol.
No desired product detected.
Alcohol remained unchanged.
d

CHEMICAL FIXATION OF CO
2
861
no desired products were detected when n-butylamine reacted with secondary or pri-
mary propargylic alcohols (entries 11 and 12), which suggested that such reaction
seems to be specific only for tertiary alcohols.
In conclusion, we have disclosed that 4-methylene-1,3-oxazolidin-2-ones could
be synthesized via the cycloadditon reaction of propargylic alcohols with primary
amines and CO under atmospheric pressure in the absence of any additional sol-
2
vent. The solvent-free methodology described herein is an ecofriendly, mild, and easy
approach to chemical fixation of CO2.
EXPERIMENTAL
All starting materials and catalysts were commercially purchased and used
1
without further purification. H NMR spectra were recorded on a Bruker DRX-
4
00 spectrometer using CDCl as solvent and tetramethylsilane (TMS) as an internal
3
standard. Mass spectra were recorded on a Shimadzu GCMS-QP5050A at an ioniza-
tion voltage of 70 eV equipped with a DB-WAX capillary column (internal diame-
ter ¼ 0.25 mm, length ¼ 30 m). Infrared (IR) spectra were recorded on an Analect
RFX-65A spectrometer.
General Procedure for the Preparation of 4-Methylene-1,3-
oxazolidin-2-ones
A mixture of propargylic alcohol (2 mmol), amine (4 mmol), and catalyst
0.1 mmol) was stirred under atmospheric CO pressure at the selected temperature
(
for the required reaction time. When the reaction was complete, the residuel was
2
flushed with Et2O (3 ꢁ 10 mL). The products were purified by column chromato-
1
graphy (gel, petroleum ether=ethyl acetate, 6:1) and identified by H NMR, mass
and IR.
Data
3
-Butyl-5,5-dimethyl-4-methyleneoxazolidin-2-one (3a). Orange oil; MS:
þ
m=z ¼ 183 (M , 34), 141 (27), 128 (43), 96 (31), 84 (18), 43 (10), 32 (24), 28 (100); IR
ꢂ1
1
(
KBr, v=cm ): 2985, 2877, 1733, 1681; H NMR (400 MHz, CDCl ) d (ppm): 0.93
3
(
3
t, J ¼ 7.4 Hz, 3H), 1.29–1.41 (m, 2H), 1.40–1.63 (m, 8H), 3.42 (t, J ¼ 7.4 Hz, 2H),
.96 (d, J ¼ 2.8 Hz, 1H), 4.05 (d, J ¼ 2.8 Hz, 1H).
3
-sec-Butyl-5,5-dimethyl-4-methyleneoxazolidin-2-one (3b). Orange oil;
þ
ꢂ1
MS: m=z ¼ 183 (M , 18), 128 (100), 110 (22), 84 (48), 41 (13); IR (KBr, v=cm ):
1
2
1
981, 2881, 1767, 1674; H NMR (400 MHz, CDCl ) d (ppm): 0.85–0.90 (m, 3H),
3
.34–1.39 (m, 3H), 1.45 (s, 6H), 1.60–1.64 (m, 2H), 3.78–3.84 (m, 1H), 3.94 (d,
J ¼ 2.8 Hz, 1H), 4.15 (d, J ¼ 2.8 Hz, 1H).
3
-Allyl-5,5-dimethyl-4-methyleneoxazolidin-2-one (3c). Orange oil; MS:
þ
m=z ¼ 167 (M , 90), 122 (100), 108 (96), 82 (50), 55 (57), 41 (48), 28 (68); IR
ꢂ1
1
(
KBr, v=cm ): 2988, 2941, 1734, 1648; H NMR (400 MHz, CDCl ) d (ppm):
3
1
5
.50 (s, 6H), 3.97 (d, J ¼ 2.8 Hz, 1H), 4.04–4.06 (m, 3H), 5.10–5.22 (m, 2H),
.68–5.89 (m, 1H).

862
J. XU ET AL.
3
-Cyclohexyl-5,5-dimethyl-4-methyleneoxazolidin-2-one
þ
(3d). White
ꢀ
solid, mp 54–56 C; MS: m=z ¼ 209 (M , 23), 128 (100), 112 (15), 84 (45), 55 (17),
ꢂ1
1
4
1 (15); IR (KBr, v=cm ): 2934, 2859, 1733, 1682; H NMR (400 MHz, CDCl ) d
3
(
ppm): 1.09–1.19 (m, 1H), 1.27–1.35 (m, 2H), 1.44 (6H, s), 1.65 (d, J ¼ 9.4 Hz,
H), 1.80 (d, J ¼ 10.4 Hz, 2H), 2.02–2.05 (m, 2H), 3.52 (1H, m), 3.95 (d, J ¼ 2.8 Hz,
Hz, 1H), 4.16 (d, J ¼ 2.8 Hz, 1H).
3
3
-n-Butyl-5,5-pentamethylene-4-methyleneoxazolidin-2-one (3e). White
þ
ꢀ
solid, mp 60–62 C; MS: m=z ¼ 223 (M , 38), 181 (58), 168 (100), 122 (25), 112
ꢂ1
1
38), 55 (11), 41 (13); IR (KBr, v=cm ): 2940, 2868, 1730, 1672; H NMR
(
(
400 MHz, CDCl ) d (ppm): 0.92 (t, J ¼ 7.4 Hz, 3H), 1.23–1.84 (m, 14H), 3.41 (t,
3
J ¼ 7.2 Hz, 2H), 3.92 (d, J ¼ 2.4 Hz, 1H), 4.00 (d, J ¼ 2.4 Hz, 1H).
3
-Butyl-5-methyl-4-methylene-5-phenyloxazolidin-2-one (3f). Orange-
þ
red oil; MS: m=z ¼ 245 (M , 20), 190 (22), 158 (100), 144 (100), 129 (32), 97 (65),
ꢂ1
7 (23), 41 (8); IR (KBr, v=cm ): 2934, 2868, 1760; H NMR (400 MHz, CDCl )
3
1
7
d (ppm): 0.88–0.94 (m, 3H), 1.30–1.34 (m, 2H), 1.55–1.60 (m, 2H), 1.85 (s, 3H),
.42–3.51 (m, 2H), 4.08 (d, J ¼ 2.8 Hz, 1H), 4.22 (d, J ¼ 3.2 Hz, 1H), 7.31–7.45
m, 5H).
3
(
3
-Butyl-5-isopropyl-5-methyl-4-methyleneoxazolidin-2-one (3g). Orange-
þ
red oil; MS: m=z ¼ 211 (M , 32), 169 (90), 126 (29), 112 (100), 84 (10), 55 (14), 41
ꢂ1
1
(
22); IR (KBr, v=cm ): 2970, 2879, 1775, 1673; H NMR (400 MHz, CDCl ) d
3
(ppm): 0.88–0.99 (m, 9H), 1.30–1.36 (m, 2H), 1.44 (s, 3H), 1.53–1.57 (m, 2H),
1
4
.80–1.82 (m, 1H), 3.31–3.38 (m, 1H), 3.43–3.57 (m, 1H), 3.91 (d, J ¼ 2.8 Hz, 1H),
.08 (d, J ¼ 2.8 Hz, 1H).
3
-Butyl-5-hexyl-5-methyl-4-methyleneoxazolidin-2-one (3h). Dark-red
þ
oil; MS: m=z ¼ 253 (M , 5), 169 (100), 126 (25), 113 (30), 98 (38), 55 (10), 41 (12);
ꢂ1
1
IR (KBr, v=cm ): 2930, 2865, 1675; H NMR (400 MHz, CDCl ) d (ppm): 0.85
3
(
3
t, J ¼ 6.8 Hz, 3H), 0.93 (t, J ¼ 7.2 Hz, 3H), 1.23–1.35 (m, 10H), 1.44–1.64 (m, 5H),
.42 (M, 2H), 3.90 (d, J ¼ 2.8 Hz, 1H), 4.07 (d, J ¼ 2.8 Hz, 1H).
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