Formation of N-sulfonylcarbamates from epichlorohydrin: Synthesis of polyfunctional oxazolidin-2-ones

Article abstract of DOI:10.1080/00397910701396922

The addition of 3-methylbut-2-enoic acid-3-bromo-2-hydroxypropyl ester 2 and 1-bromo-3-phenylsulfanyl propan-2-ol 3, obtained from epichlorohydrin, to aroxy and alkoxysulfonyl isocyanates 1 in anhydrous ether at ambient temperature affords the correspondi

Full text of DOI:10.1080/00397910701396922

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Formation of N‐Sulfonylcarbamates from
Epichlorohydrin: Synthesis of Polyfunctional
Oxazolidin‐2‐ones
Hamdi Rmedi a , Mohamed Béji b & Ahmed Baklouti a
a Faculty of Sciences of Tunis, Laboratory of Structural Organic Chemistry ,
University of Tunis—El Manar , Tunis, Tunisia
b Preparatory Institute for Engineering Studies of Tunis (IPEIT) , Tunis,
Tunisia
Published online: 03 Jul 2007.
To cite this article: Hamdi Rmedi , Mohamed Béji & Ahmed Baklouti (2007) Formation of
N‐Sulfonylcarbamates from Epichlorohydrin: Synthesis of Polyfunctional Oxazolidin‐2‐ones, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:13,
2215-2223, DOI: 10.1080/00397910701396922
To link to this article: http://dx.doi.org/10.1080/00397910701396922
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Synthetic Communicationsw, 37: 2215–2223, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701396922
Formation of N-Sulfonylcarbamates from
Epichlorohydrin: Synthesis of
Polyfunctional Oxazolidin-2-ones
Hamdi Rmedi
Faculty of Sciences of Tunis, Laboratory of Structural Organic Chemistry,
University of Tunis—El Manar, Tunis, Tunisia
´
Mohamed Beji
Preparatory Institute for EngineeringStudiesofTunis(IPEIT), Tunis, Tunisia
Ahmed Baklouti
Faculty of Sciences of Tunis, Laboratory of Structural Organic
Chemistry, University of Tunis—El Manar, Tunis, Tunisia
Abstract: The addition of 3-methylbut-2-enoic acid-3-bromo-2-hydroxypropyl ester 2
and 1-bromo-3-phenylsulfanyl propan-2-ol 3, obtained from epichlorohydrin, to aroxy
and alkoxysulfonyl isocyanates 1 in anhydrous ether at ambient temperature affords the
corresponding N-sulfonyl bromocarbamates 4. These are treated with triethylamine in
refluxing acetone to give exclusively the corresponding polyfunctional oxazolidin-2-
ones 5 with good yields.
Keywords: aroxy and alkoxysulfonyl isocyanates, N-sulfonyl bromocarbamates,
oxazolidin-2-one
INTRODUCTION
The addition of hydroxyl compounds, particularly b-bromoalcohols in alkali
media, to isocyanates generally led to oxazolidinones. These compounds
Received in Poland October 4, 2006
Address correspondence to Hamdi Rmedi, Faculty of Sciences of Tunis, Laboratory
of Structural Organic Chemistry, University of Tunis—El Manar, 1092 Tunis, Tunisia.
E-mail: hamdiram@yahoo.fr
2215

´
H. Rmedi, M. Beji, and A. Baklouti
2216
are widely studied because of their biological and pharmacological
properties.[1–4]
These heterocyclic compounds may be obtained by the action of
threonine on trichloromethyl carbonate,[5] whereas other oxazolidinones
were obtained by the condensation reaction of g-hydroxyesters or g-hydroxy-
sulfones on tosylisocyanate.[6]
In a previous work related to the synthesis of new N-sulfonylcarbamates
that may have important biological properties, we have studied the reactivity
of aroxy and alkoxysulfonyl isocyanates toward fluorinated and highly fluori-
nated alcohols,[7,8] F-alkylthiols,[8] and polyfluorinated aminoalcohols.[9]
Here we extend their reactivity to 3-methylbut-2-enoic acid-3-bromo-2-
hydroxypropyl ester and 1-bromo-3-phenylsulfanylpropan-2-ol to synthesize
new bromocarbamates. These carbamates undergo ring formation, by action
of triethylamine in refluxing acetone, to afford N-aroxy and alkoxysulfonyl
oxazolididin-2-ones.
RESULTS AND DISCUSSION
In this work we describe an efficient method to synthesize new polyfunctional
oxazolidin-2-ones starting from bromo derivatives 2 and 3.[10] The latter have
been obtained from epichlorohydrin. This allows an easy substitution at the C5
position of the oxazolidinone ring to easily obtain different substituted
oxazolidinones.
The 3-methylbut-2-enoic acid-3-bromo-2-hydroxypropyl ester 2 reacts
easily at ambient temperature, in anhydrous ether and under a nitrogen atmos-
phere with N-aroxy and alkoxysulfonyl isocyanates 1a–g to give the corre-
sponding N-sulfonyl bromocarbamates 4a–g (see Table 1). These
carbamates, described for the first time, have an additional reactivity
because of the presence of the bromine atom. For instance, the action of
Table 1. Yields and times of N-sulfonylbro-
mocarbamates 4a–j
Carbamates
Yield (%)
Time (min)
4a
4b
4c
4d
4e
4f
92
86
84
93
92
95
90
94
92
95
2
4
2
5
3
1
1
2
5
2
4g
4h
4i
4j

N-Sulfonylcarbamates from Epichlorohydrin
2217
Scheme 1.
triethylamine in refluxing acetone led to the intramolecular cyclization
reaction yielding oxazolidin-2-ones 5a–g as outlined in Scheme 1.
In a similar manner, the 1-bromo-3-phenylsulfanyl propan-2-ol 3 reacts in
anhydrous ether, at room temperature, with N-sulfonylisocyanates 1a–c to
afford the corresponding bromo carbamates 4h–j. Next, the oxazolidin-2-
one ring was formed by the action of the triethylamine to obtain 5h–j in
moderate yields (Scheme 1). The different data for the synthesis and charac-
terization of the carbamates 4a–j and oxazolidin-2-ones 5a–j are summarized
respectively in Tables 1 and 2.
It is worth noting that the chlorohomologues of 2 and 3 may be obtained
in one step, on treatment of epichlorohydrin with acrylic acid and thiophenol
Table 2. Yields and times of polyfunctional
oxazolidin-2-ones 5a–j
Oxazolidinones
Yield (%)
Time (h)
5a
5b
5c
5d
5e
5f
80
88
72
79
76
84
86
78
87
73
1.5
2
2
2
2
1.5
1
5g
5h
5i
2
2
5j
2

´
H. Rmedi, M. Beji, and A. Baklouti
2218
in acidic media respectively.[11] The addition reaction of these compounds
with N-sulfonylisocyanates is easily performed to yield the corres-
ponding chlorocarbamates, but given the less nucleofuge character of the
chlorine atom, the cyclization reaction leads to much lower yields (less than
15%).
EXPERIMENTAL
NMR spectra were recorded on an Ac 300 Bruker instrument at 300 MHz
for 1H in TMS as internal reference. IR spectra (CHCl3) were recorded
on a Perkin-Elmer Paragon 1000 PC. Mass spectra were obtained by
negative and positive modes of electrospray ionization (ESI NEG,
ESI POS). Aroxy and alkoxysulfonyl isocyanates 1a–g were prepared by
the action of corresponding phenols and alcohols on chlorosulfonyl isocya-
nate.[12] Bromoderivates 2 and 3 were prepared following a method
described in the literature.[10]
Synthesis of N-Sulfonyl Bromocarbamates 4a–j
To 10 mmol of aroxy(alkoxy)sulfonyl isocyanates 1a–g dissolved in 10 mL of
ether, 10 mmol of the bromoderivate 2 or 3 dissolved in 10 mL of the same
solvent were added. The mixture was then stirred for 1 to 5 min (depending
on the nature of isocyanate used) at ambient temperature and under a
nitrogen atmosphere. The solvent was evaporated in vacuum, and the
products were isolated by column chromatography as viscous oils (eluant:
ethylic ether 30%, petroleum ether 70%).
Data
4a: IR (n, cm21): 3360 (NH), 1767 (C55O), 1719 (C55O), 1649 (C55C),
1393–1175 (SO2); 1H NMR (d, ppm): 9.00 (1H, NH), 7.20 (4H, arom,
3J ¼ 8.8 Hz), 5.70 (1H, CH55C), 5.25 (1H, CH-O), 4.30 (2H,
2
3
3
CH2-O, Jab ¼ 12.4 Hz, Jax ¼ 6.2 Hz, Jbx ¼ 4.1 Hz), 3.55 (2H, CH2-Br,
3
3
2Jab ¼ 12.1 Hz, Jax ¼ 5.9 Hz, Jbx ¼ 4.8 Hz), 2.15 (3H, CH3), 1.90 (3H,
CH3); 13C NMR (d, ppm): 20.4, 27.6, 34.4, 62.1, 73.9, 114.7, 123.3, 129.9,
133.6, 148.1, 149.5, 159.9, 166.1; HRMS [M-H]2: calcd. 467.9519, found
467.9526.
4b: IR (n, cm21): 3359 (NH), 1766 (C55O), 1718 (C55O), 1648 (C55C),
1
1390–1172 (SO2); H NMR (d, ppm): 9.10 (1H, NH), 6.80 (2H, arom),
2
5.65 (1H, CH55C), 5.20 (1H, CH-O), 4.30 (2H, CH2-O, Jab ¼ 12.4 Hz,
3Jax ¼ 6.3 Hz, 3Jbx ¼ 4.1 Hz), 3.50 (2H, CH2-Br, 2Jab ¼ 12.3 Hz,
3
3Jax ¼ 5.8 Hz, Jbx ¼ 4.6 Hz), 2.35 [6H, 2(CH3)], 2.25 (3H, CH3), 2.15 (3H,

N-Sulfonylcarbamates from Epichlorohydrin
2219
CH3), 1.90 (3H, CH3); 13C NMR (d, ppm): 17.1, 20.4, 20.6, 27.5, 34.4, 62.2,
73.8, 114.9, 129.9, 131.3, 136.3, 145.9, 149.5, 159.1, 166.1; HRMS [M-H]2:
calcd. 476.0378, found 476.0383.
4c: IR (n, cm21): 3352 (NH), 1763 (C55O), 1716 (C55O), 1648 (C55C),
1
1399–1177 (SO2); H NMR (d, ppm): 9.15 (1H, NH), 5.70 (1H, CH55C),
5.20 (1H, CH-O), 4.90 (2H, CCl3-CH2-O), 4.35 (2H, CH2-O,
2Jab ¼ 12.4 Hz, 3Jax ¼ 6.2 Hz, 3Jbx ¼ 4.3 Hz), 3.55 (2H, CH2-Br,
3
3
2Jab ¼ 12.1 Hz, Jax ¼ 5.9 Hz, Jbx ¼ 4.8 Hz), 2.20 (3H, CH3), 1.95 (3H,
CH3); 13C NMR (d, ppm): 20.4, 27.5, 34.5, 62.1, 73.8, 80.8, 92.9, 114.9,
149.8, 159.2, 165.9; HRMS [M-H]2: calcd. 487.8739, found 487.8753.
4d: IR (n, cm21): 3362 (NH), 1768 (C55O), 1719 (C55O), 1648 (C55C),
1
1396–1172 (SO2); H NMR (d, ppm): 9.30 (1H, NH), 7.35 (5H, arom),
2
5.65 (1H, CH55C), 5.20 (1H, CH-O), 4.25 (2H, CH2-O, Jab ¼ 12.3 Hz,
3Jax ¼ 6.3 Hz, 3Jbx ¼ 4.2 Hz), 3.50 (2H, CH2-Br, 2Jab ¼ 12.1 Hz,
3
3Jax ¼ 5.9 Hz, Jbx ¼ 4.7 Hz), 2.10 (3H, CH3), 1.90 (3H, CH3); 13C NMR
(d, ppm): 20.5, 27.6, 34.3, 62.2, 73.7, 114.8, 121.6, 127.2, 130.1, 149.3,
149.8, 159.5, 166.1; HRMS [M-H]2: calcd. 433.9909, found 433.9917.
4e: IR (n, cm21): 3360 (NH), 1767 (C55O), 1719 (C55O), 1649 (C55C),
1393–1175 (SO2); 1H NMR (d, ppm): 9.00 (1H, NH), 7.20 (4H, arom,
3J ¼ 8.8 Hz), 5.70 (1H, CH55C), 5.25 (1H, CH-O), 4.30 (2H, CH2-O,
2Jab ¼ 12.1 Hz, 3Jax ¼ 6.4 Hz, 3Jbx ¼ 4.3 Hz), 3.55 (2H, CH2-Br,
3
3
2Jab ¼ 12.2 Hz, Jax ¼ 5.8 Hz, Jbx ¼ 4.8 Hz), 2.30 (3H, CH3), 2.15 (3H,
CH3), 1.90 (3H, CH3); 13C NMR (d, ppm): 20.5, 20.9, 27.5, 34.4, 62.1,
73.7, 114.9, 121.5, 130.5, 138.3, 147.6, 149.2, 159.5, 166.0; HRMS [M-
H]2: calcd. 448.0065, found 448.0082.
4f: IR (n, cm21): 3358 (NH), 1769 (C55O), 1719 (C55O), 1649
(C55C), 1396–1174 (SO2); 1H NMR (d, ppm): 9.10 (1H, NH), 7.30
(4H, arom), 5.70 (1H, CH55C), 5.30 (1H, CH-O), 4.30 (2H, CH2-O,
2Jab ¼ 12.3 Hz, 3Jax ¼ 6.4 Hz, 3Jbx ¼ 4.2 Hz), 3.55 (2H, CH2-Br,
3
3
2Jab ¼ 12.1 Hz, Jax ¼ 5.9 Hz, Jbx ¼ 4.7 Hz), 2.15 (3H, CH3), 1.90 (3H,
CH3); 13C NMR (d, ppm): 20.4, 27.6, 34.4, 62.2, 73.8, 114.8, 116.0,
124.0, 146.5, 149.6, 159.9, 160.8, 166.1; HRMS [M-H]2: calcd.
451.9814, found 451.9814.
4g: IR (n, cm21): 3353 (NH), 1768 (C55O), 1719 (C55O), 1649 (C55C),
1
1408–1177 (SO2); H NMR (d, ppm): 9.20 (1H, NH), 7.20 (2H, arom),
2
5.75 (1H, CH55C), 5.25 (1H, CH-O), 4.25 (2H, CH2-O, Jab ¼ 12.4 Hz,
3Jax ¼ 6.4 Hz, 3Jbx ¼ 4.1 Hz), 3.55 (2H, CH2-Br, 2Jab ¼ 12.1 Hz,
3
3Jax ¼ 5.7 Hz, Jbx ¼ 4.7 Hz), 2.15 (3H, CH3), 1.90 (3H, CH3); 13C NMR
(d, ppm): 20.4, 27.5, 34.6, 62.3, 73.8, 114.9, 129.1, 130.5, 133.5, 142.9,
149.3, 159.1, 166.1; HRMS [M-H]2: calcd. 535.8739, found 535.8752.

´
H. Rmedi, M. Beji, and A. Baklouti
2220
4h: IR (n, cm21): 3362 (NH), 1765 (C55O), 1397–1174 (SO2); 1H NMR(d, ppm):
8.65 (1H, NH), 7.30 (5H, arom), 7.25 (4H, arom, 3J ¼ 8.8 Hz), 4.15 (1H, CH-O),
3.60 (2H, CH2-Br, 2Jab ¼ 12.8 Hz, 3Jax ¼ 8.5 Hz, 3Jbx ¼ 5.1 Hz), 3.40 (2H, CH2-
S, 2Jab ¼ 9.1 Hz, 3Jax ¼ 4.3 Hz, 3Jbx ¼ 3.8 Hz); 13C NMR (d, ppm): 38.1, 54.5,
68.2, 123.4, 127.4, 129.5, 129.9, 130.3, 133.2, 133.5, 148.1, 149.6; HRMS [M-
H]2: calcd. 477.9185, found 477.9186.
1
4i: IR (n, cm21): 3357 (NH), 1765 (C55O), 1393–1173 (SO2); H NMR (d,
ppm): 8.55 (1H, NH), 7.30 (5H, arom), 6.80 (2H, arom), 4.20 (1H, CH-O),
2
3
3
3.60 (2H, CH2-Br, Jab ¼ 12.9 Hz, Jax ¼ 8.3 Hz, Jbx ¼ 5.0 Hz), 3.40 (2H,
2
3
3
CH2-S, Jab ¼ 8.9 Hz, Jax ¼ 4.2 Hz, Jbx ¼ 3.6 Hz), 2.30 [6H, 2(CH3)],
2.20 (3H, CH3); 13C NMR (d, ppm): 17.1, 20.7, 38.5, 54.6, 68.1, 127.6,
129.4, 129.9, 130.5, 131.4, 133.2, 136.5, 145.8, 149.8; HRMS [M-H]2:
calcd. 486.0044, found 486.0054.
1
4j: IR (n, cm21): 3354 (NH), 1764 (C55O), 1400–1174 (SO2); H NMR (d,
ppm): 8.90 (1H, NH), 7.30 (5H, arom), 4.90 (2H, CCl3-CH2-O), 4.15 (1H,
2
3
3
CH-O), 3.60 (2H, CH2-Br, Jab ¼ 12.8 Hz, Jax ¼ 8.5 Hz, Jbx ¼ 5.2 Hz),
2
3
3
3.35 (2H, CH2-S, Jab ¼ 8.9 Hz, Jax ¼ 4.3 Hz, Jbx ¼ 3.9 Hz); 13C NMR
(d, ppm): 38.2, 54.5, 68.3, 80.9, 92.8, 127.5, 129.4, 130.2, 133.1, 149.8;
HRMS [M-H]2: calcd. 497. 8405, found 497.8413.
Synthesis of N-Sulfonyl Oxazolidin-2-ones 5a–j
To 10 mmol of N-sulfonyl bromocarbamates 4a–j in acetone solution,
10 mmol of triethylamine were added dropwise with stirring. The mixture
was stirred at 608C for 1 to 2 h. The precipitate of triethylammonium
bromide that formed was filtered. The organic solution was evaporated
in vacuum, and the residue was purified by column chromatography to give
N-sulfonyloxazolidin-2-ones 5a–j as very viscous oils (eluant: ethylic ether
20%, cyclohexane 80%).
Data
5a: IR (n, cm21): 1803 (C55O), 1721 (C55O), 1647 (C55C), 1396–1182
1
3
(SO2); H NMR (d, ppm): 6.85 (4H, arom, J ¼ 8.8 Hz), 5.55 (1H, CH55C),
2
3
4.75 (1H, CH-O), 4.20 (2H, CH2-O, Jab ¼ 12.5 Hz, Jax ¼ 4.1 Hz,
2
3
3
3Jbx ¼ 3.0 Hz), 3.80 (2H, CH2-N, Jab ¼ 9.2 Hz, Jax ¼ 8.8 Hz, Jbx¼
6.6 Hz), 2.10 (3H, CH3), 1.80 (3H, CH3); 13C NMR (d, ppm): 20.5, 27.5,
47.7, 62.3, 72.3, 114.3, 123.1, 129.4, 134.0, 147.7, 150.8, 160.8, 166.1;
HRMS [M þ Na]þ: calcd. 412.0233, found 412.0241.
5b: IR (n, cm21): 1804 (C55O), 1718 (C55O), 1646 (C55C), 1392–1176
(SO2); 1H NMR (d, ppm): 6.80 (2H, arom), 5.65 (1H, CH55C),

N-Sulfonylcarbamates from Epichlorohydrin
2221
2
3
4.80 (1H, CH-O), 4.25 (2H, CH2-O, Jab ¼ 12.5 Hz, Jax ¼ 4.1 Hz,
3Jbx ¼ 3.1 Hz), 4.05 (2H, CH2-N, 2Jab ¼ 9.2 Hz, 3Jax ¼ 8.6 Hz,
3Jbx ¼ 6.5 Hz), 2.30 [6H, 2(CH3)], 2.20 (3H, CH3), 2.10 (3H, CH3), 1.80
(3H, CH3); 13C NMR (d, ppm): 17.1, 20.3, 20.6, 27.4, 47.5, 62.3,
72.0, 114.7, 129.8, 131.2, 136.2, 145.2, 150.5, 159.8, 165.8; HRMS
[M þ Na]þ: calcd. 420.1092, found 420.1098.
5c: IR (n, cm21): 1798 (C55O), 1713 (C55O), 1648 (C55C), 1378–1190
1
(SO2); H NMR (d, ppm): 5.70 (1H, CH55C), 5.00 (2H, CCl3-CH2-O), 4.95
2
3
3
(1H, CH-O), 4.35 (2H, CH2-O, Jab ¼ 12.4 Hz, Jax ¼ 4.2 Hz, Jbx
¼
2
3
3
3.3 Hz), 4.10 (2H, CH2-N, Jab ¼ 9.3 Hz, Jax ¼ 8.8 Hz, Jbx ¼ 6.5 Hz),
2.20 (3H, CH3), 1.90 (3H, CH3); 13C NMR (d, ppm): 20.4, 27.5, 47.2, 62.2,
72.6, 81.3, 92.8, 114.4, 150.1, 160.0, 165.8; HRMS [M þ Na]þ: calcd.
431.9454, found 431.9465.
5d: IR (n, cm21): 1803 (C55O), 1719 (C55O), 1648 (C55C), 1380–1187
1
(SO2); H NMR (d, ppm): 7.35 (5H, arom), 5.60 (1H, CH55C), 4.80 (1H,
2
3
3
CH-O), 4.20 (2H, CH2-O, Jab ¼ 12.5 Hz, Jax ¼ 4.1 Hz, Jbx ¼ 3.0 Hz),
2
3
3
3.85 (2H, CH2-N, Jab ¼ 9.2 Hz, Jax ¼ 8.5 Hz, Jbx ¼ 6.5 Hz), 2.15 (3H,
CH3), 1.85 (3H, CH3); 13C NMR (d, ppm): 20.3, 27.5, 47.8, 62.3, 72.3,
114.7, 121.6, 128.3, 130.3, 149.4, 150.6, 159.7, 166.2; HRMS [M þ Na]þ:
calcd. 378.0623, found 378.0625.
5e: IR (n, cm21): 1805 (C55O), 1719 (C55O), 1649 (C55C), 1395–1173
1
3
(SO2); H NMR (d, ppm): 7.15 (4H, arom, J ¼ 8.8 Hz), 5.60 (1H, CH55C),
2
3
5.15 (1H, CH-O), 4.15 (2H, CH2-O, Jab ¼ 12.4 Hz, Jax ¼ 4.1 Hz,
3Jbx ¼ 3.3 Hz), 3.80 (2H, CH2-N, 2Jab ¼ 9.2 Hz, 3Jax ¼ 8.8 Hz,
3Jbx ¼ 6.6 Hz), 2.30 (3H, CH3), 2.10 (3H, CH3), 1.85 (3H, CH3); 13C NMR
(d, ppm): 20.5, 20.8, 27.6, 48.0, 62.2, 73.8, 114.8, 121.5, 130.6, 138.4,
147.5, 150.8, 159.4, 166.1; HRMS [M þ Na]þ: calcd. 392.0779, found
392.0786.
5f: IR (n, cm21): 1804 (C55O), 1722 (C55O), 1647 (C55C), 1396–1182
1
(SO2); H NMR (d, ppm): 6.95 (4H, arom), 5.55 (1H, CH55C), 4.75 (1H,
2
3
3
CH-O), 4.20 (2H, CH2-O, Jab ¼ 12.5 Hz, Jax ¼ 4.2 Hz, Jbx ¼ 3.2 Hz),
2
3
3
3.80 (2H, CH2-N, Jab ¼ 9.2 Hz, Jax ¼ 8.7 Hz, Jbx ¼ 6.4 Hz), 2.10 (3H,
CH3), 1.80 (3H, CH3); 13C NMR (d, ppm): 20.5, 27.5, 47.7, 62.3, 72.3,
114.3, 13C NMR (d, ppm): 20.4, 27.5, 47.7, 62.3, 72.4, 114.5, 116.0, 124.0,
146.5, 150.8, 160.5, 160.8, 166.1; HRMS [M þ Na]þ: calcd. 396.0529,
found 396.0540.
5g: IR (n, cm21): 1811 (C55O), 1719 (C55O), 1648 (C55C), 1388–1173
1
(SO2); H NMR (d, ppm): 7.25 (2H, arom), 5.70 (1H, CH55C), 5.00 (1H,
2
3
3
CH-O), 4.40 (2H, CH2-O, Jab ¼ 12.5 Hz, Jax ¼ 4.1 Hz, Jbx ¼ 3.0 Hz),
2
3
3
4.20 (2H, CH2-N, Jab ¼ 9.4 Hz, Jax ¼ 8.6 Hz, Jbx ¼ 6.6 Hz), 2.20 (3H,

´
H. Rmedi, M. Beji, and A. Baklouti
2222
CH3), 1.95 (3H, CH3); 13C NMR (d, ppm): 20.5, 27.5, 47.3, 62.0, 72.2, 114.4,
129.3, 130.6, 133.9, 142.1, 150.0, 158.9, 165.7; HRMS [M þ Na]þ: calcd.
479.9454, found 479.9463.
1
5h: IR (n, cm21): 1802 (C55O), 1365–1179 (SO2); H NMR (d, ppm): 7.30
(5H, arom), 6.90 (4H, arom, 3J ¼ 8.8 Hz), 4.65 (1H, CH-O), 3.90 (2H,
2
3
3
CH2-N, Jab ¼ 10.7 Hz, Jax ¼ 8.6 Hz, Jbx ¼ 6.4 Hz), 3.10 (2H, CH2-S,
3
3
2Jab ¼ 9.0 Hz, Jax ¼ 4.2 Hz, Jbx ¼ 3.2 Hz); 13C NMR (d, ppm): 50.1,
56.8, 73.1, 123.3, 127.5, 129.4, 129.8, 130.1, 133.2, 133.7, 147.9, 151.0;
HRMS [M þ Na]þ: calcd. 421.9899, found 421.9903.
1
5i: IR (n, cm21): 1805 (C55O), 1378–1192 (SO2); H NMR (d, ppm): 7.30
(5H, arom), 6.80 (2H, arom), 4.70 (1H, CH-O), 4.05 (2H, CH2-N,
2Jab ¼ 10.9 Hz, 3Jax ¼ 8.6 Hz, 3Jbx ¼ 6.5 Hz), 3.30 (2H, CH2-S,
3
3
2Jab ¼ 8.9 Hz, Jax ¼ 4.1 Hz, Jbx ¼ 3.0 Hz), 2.30 [6H, 2(CH3)], 2.20 (3H,
CH3); 13C NMR (d, ppm): 17.2, 20.7, 50.0, 56.8, 74.1, 127.2, 129.3, 129.6,
130.2, 131.5, 133.0, 136.4, 145.7, 150.8; HRMS [M þ Na]þ: calcd. 430.
0758, found 430.0764.
1
5j: IR (n, cm21): 1797 (C55O), 1395–1184 (SO2); H NMR (d, ppm): 7.30
(5H, arom), 4.95 (2H, CCl3-CH2-O), 4.75 (1H, CH-O), 4.10 (2H, CH2-N,
3
3
2
2Jab ¼ 10.8 Hz, Jax ¼ 8.5 Hz, Jbx ¼ 6.5 Hz), 3.25 (2H, CH2-S, Jab ¼
9.1 Hz, Jax ¼ 4.2 Hz, Jbx ¼ 3.2 Hz); 13C NMR (d, ppm): 49.7, 57.0, 74.8,
81.5, 92.7, 127.6, 129.2, 130.3, 133.5, 151.1; HRMS [M þ Na]þ: calcd.
441.9120, found 441.9127.
3
3
CONCLUSION
As shown in Table 2, a series of new compounds with different substitutions
on nitrogen and the C5 position of the oxazolidin-2-one ring was prepared and
may allow the establishment of structure–activity relationships. This will be
done in collaboration with appropriate laboratories.
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