Synthesis of N-vinyl-2-oxazolidone: A commercially important intermediate

Article abstract of DOI:10.1081/SCC-100104422

An improved synthesis of N-vinyl-2-oxazolidone starting from ethanolamine has been developed.

Full text of DOI:10.1081/SCC-100104422

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SYNTHESIS OF N-VINYL-2-OXAZOLIDONE: A
COMMERCIALLY IMPORTANT INTERMEDIATE*
Parimi V. S. N. Vani a , Asiya Seema Chida a , Rajagopal Srinivasan a , Malapaka
Chandrasekharam a & Ashok Kumar Singh b
a Bio-Organic Laboratory, Division of Organic Chemistry-III, Indian Institute of Chemical
Technology, Hyderabad, 500 007, India
b Bio-Organic Laboratory, Division of Organic Chemistry-III, Indian Institute of Chemical
Technology, Hyderabad, 500 007, India
Published online: 09 Nov 2006.
To cite this article: Parimi V. S. N. Vani , Asiya Seema Chida , Rajagopal Srinivasan , Malapaka Chandrasekharam & Ashok
Kumar Singh (2001): SYNTHESIS OF N-VINYL-2-OXAZOLIDONE: A COMMERCIALLY IMPORTANT INTERMEDIATE* , Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:13, 2043-2046
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SYNTHETIC COMMUNICATIONS, 31(13), 2043–2046 (2001)
SYNTHESIS OF N-VINYL-2-OXAZOLIDONE:
A COMMERCIALLY IMPORTANT
INTERMEDIATE*
Parimi V. S. N. Vani, Asiya Seema Chida,
Rajagopal Srinivasan, Malapaka Chandrasekharam,
and Ashok Kumar Singh{
Bio-Organic Laboratory, Division of Organic Chemistry-III,
Indian Institute of Chemical Technology,
Hyderabad-500 007, India
ABSTRACT
An improved synthesis of N-vinyl-2-oxazolidone starting
from ethanolamine has been developed.
Despite the extensive uses of N-vinyl-2-oxazolidone based polymers in
the cosmetics,1a photographic materials,1b detergents,1c,d jet fuels, diesel
fuels, furnace oils and lubricants1e to mention a few, the preparation of
N-vinyl-2-oxazolidone has not been exploited for the large-scale synthesis.
Even the reports related to the laboratory scale syntheses are found to be a
few in the literature.2 In this report we described the improved synthesis of
the title compound.
N-(20-hydroxyethyl)-2-oxazolidone (2) is obtained by refluxing
diethanolamine in diethyl carbonate and sodium methoxide for 2 h
and it was used for the next conversion without further purification.
*IICT communication number 4470.
{Corresponding author.
2043
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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VANI ET AL.
The N-(20-hydroxyethyl)-2-oxazolidone was treated with SOCl2 in benzene
in presence of pyridine used as HCl scavenger. Stirring for 4 h and filtration
of pyridinium hydrochloride afforded N-(20-chloroethyl)-2-oxazolidone. In
this step, the reaction time has been reduced drastically compared to the
previously reported procedure.2 A simple and convenient work up pro-
cedure has been developed to isolate the expected product without any
1
loss of material. The disappearance of triplet at d 3.80in H-NMR spectrum
and the absence of absorption band due to hydroxyl group in IR spectrum
support the formation of compound 3.
When compound 3 was subjected to dehydrohalogenation using
sodium methoxide at various temperatures in methanol gave the expected
vinyl compound 4 in 75% yield. It was found that potassium tert-butoxide
in tert-butanol is the most efficient system for the above conversion. The
1
formation of vinyl compound 4 was confirmed by IR, H-NMR and mass
1
spectra. Among the two signals for vinylic methylene protons in H-NMR
spectrum, one signal appeared as a doublet at d 4.24 and another one
merged with a signal corresponding to methylene protons of oxazolidone
ring appeared as a multiplet at d 4.33–4.51. Furthermore, a doublet of
doublet signal for H1’ appeared at d 6.83.
Scheme 1.
The preparation of N-vinyl-2-oxazolidone has been effectively
improved starting from diethanolamine in 69% overall yield. In the
second step the reported procedure2 involves approximately 30h including
workup where as this improved procedure requires only 7 h with a very
convenient and easy workup procedure.
EXPERIMENTAL
Preparation of N-(20-hydroxy ethyl)-2-oxazolidone (2). To a solution of
diethanolamine (1645.5 g, 15.67 mol) and diethyl carbonate (2310.7 g,

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N-VINYL-2-OXAZOLIDONE
2045
19.58 mol) was added NaOMe (7.8 g, 0.14 mol) in one portion and the
resulting mixture was refluxed for 2 h. Ethanol formed in the reaction was
removed by distillation under reduced pressure to give compound 2 in
quantitative yield. IR (Neat, ꢀmax) cmÀ1: 1728 (C ¼ O); 3100–3600 (OH)
1H-NMR (CDCl3/TMS) ppm: d 2.60(brs, 1H, OH); 3.44 (t, 2H, J ¼ 4 Hz,
H1’); 3.75 (t, 2H, J ¼ 9 Hz, H4); 3.82 (t, 2H, J ¼ 4 Hz, H2’); 4.38 (t, 2H,
J ¼ 9 Hz, H5) MS (m/e): 131 (Mþ); 100 (Mþ-31); 56 (Mþ-75).
N-(20-Chloroethyl)-2-oxazolidone (3). To a solution of 2 (1626.18 g,
12.41 mol) and pyridine (1078.40 g, 13.65 mol) in dry benzene (3.5 L) was
added thionylchloride (1611.0g, 13.54 mol) slowly with efficient stirring in
2 h at 30ꢀC. Stirring was continued for 4 h at the same temperature. The
reaction mixture was filtered using buchner funnel and the residue washed
with benzene (4 ꢁ 2.5 L). Solvent was removed from the filtrate and the
residue distilled under reduced pressure to obtain the pure product 3 as a
ꢀ
pale yellow liquid. Yield: 1563.0g (84.2%). b.p.: 100 C/1.0mm IR (Neat,
ꢀ
max) cmÀ1: 1744 (C ¼ O) 1H-NMR (CDCl3/TMS) ppm: d 3.57–3.76 (m, 6H,
H4, H1’ & H2’); 4.33 (t, 2H, J ¼ 9 Hz, H5) MS (m/e): 149 (Mþ); 100 (Mþ-49);
56 (Mþ-93).
N-Vinyl-2-oxazolidone(4) . To a solution of 3 (130.00 g, 0.869 mol) in
t-butanol (0.35 L) was added potassium t-butoxide (97.4 g, 0.869 mol) slowly
in portions with stirring while the reaction became exothermic. Stirring
continued for 30min and the reaction mixture washed with ethyl acetate
(3 ꢁ 1 L). Filtered and solvent removed from filtrate, the residue was dis-
tilled under reduced pressure to afford the pure product 4 as a yellow liquid.
Yield: 81.00 g (82.4%). b.p. 90ꢀC/1.4 mm IR (Neat, ꢀmax) cmÀ1: 1760
(C ¼ O); 1600 (C ¼ C) 1H-NMR (CDCl3/TMS) ppm: d 3.69 (t, 2H,
J ¼ 9 Hz, H5); 4.24 (d, 1H, J ¼ 16 Hz, Hb); 4.33–4.51 (m, 3H, H5 & Ha);
6.83 (dd, 1H, J ¼ 16 &10Hz, H 1’) MS (m/e): 113 (Mþ).
ACKNOWLEDGMENT
PVSNV and ASC thank Dr. K. V. Raghavan, Director, IICT,
Hyderabad for allowing to work in this project and for financial support.
REFERENCES
1. (a) Moeller, H.; Osberghaus, R.; Budnowski, M. (Henkel K-G. a. A).
Ger. Offen. 2704904, 1977. (b) Chujo, K.; Sakaguchi, S.; Tsuji, N.
(Fuji Photo Film Co., Ltd.) Japan Koka, 77102722, 1977. (c) Waldhoff,
H.; Schmadel, E.; Engelskirchen, K.; Galinke, J. (Henkel K-G. a. A).

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VANI ET AL.
Ger. Offen. 2814329, 980. (d) Ibid. Ger. Offen. 2814287, 1980. (e)
Emmons, W. D. U.S. Patent. 3371040 (Cl.252–515), pp. 7, 1968.
2. (a) Drechsel, E. K. J. Org. Chem. 1957, 22, 849. (b) Hart, R.;
Timmerman, D. Makromol. Chem. 1959, 31, 223.
Received in the Netherlands September 13, 2000

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