A new synthetic method of 1,4-dihydro-2h-3,1-benzoxazin-2-ones: Selenium-catalyzed reductive carbonylation of aromatic nitro compounds with carbon monoxide

Article abstract of DOI:10.1055/s-2004-820018

It was confirmed that selenium catalyzed the reaction of 2-nitrobenzyl alcohols with carbon monoxide to afford 1,4-dihydro-2H-3,1-benzoxazin-2-ones in good yields. Similarly, seven-membered cyclic carbamate was prepared by the reaction of 2-(2-nitrophenyl)ethanol with carbon monoxide.

Full text of DOI:10.1055/s-2004-820018

8
86
LETTER
A New Synthetic Method of 1,4-Dihydro-2H-3,1-benzoxazin-2-ones: Selenium-
Catalyzed Reductive Carbonylation of Aromatic Nitro Compounds with
Carbon Monoxide
A
Y
N
ew Synthetic
M
u
e
thod of 1,4
t
-Dihyd
a
r
o-2
H
-3,1-
k
benzoxazin-
a
2-ones Nishiyama,* Yoshitaka Naitoh, Noboru Sonoda*
Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan
E-mail: nishiya@ipcku.kansai-u.ac.jp
Received 25 December 2003
Abstract: It was confirmed that selenium catalyzed the reaction of
OH
Se (Cat.)
OH
NCO
2
2
-nitrobenzyl alcohols with carbon monoxide to afford 1,4-dihydro-
H-3,1-benzoxazin-2-ones in good yields. Similarly, seven-mem-
+
CO
NO2
bered cyclic carbamate was prepared by the reaction of 2-(2-nitro-
phenyl)ethanol with carbon monoxide.
Key words: selenium, carbon monoxide, 1,4-dihydro-2H-3,1-ben-
O
zoxazin-2-ones, carbonylation, carbamates
N
H
O
Scheme 1
Since it has recently been shown that the thermal decar-
boxylation of 1,4-dihydro-2H-3,1-benzoxazin-2-ones
provided a useful tool for the generation of aza-ortho-xy-
using selenium, a non transition metal element, as a cata-
lyst.7 To determine the optimized reaction conditions, 2-
nitrobenzyl alcohol (1a) was treated with carbon monox-
ide in the presence of a catalytic amount of selenium un-
der various reaction conditions and these results are
shown in Table 1. When 1a was stirred at 150 °C for 5
hours under pressurized carbon monoxide (30 atm) in the
presence of N-methylpyrrolidine as a tertiary amine and a
catalytic amount of selenium (10 mol%) in THF solvent,
,8
1
lylenes, the development of a synthetic method of these
compounds has received considerable attention. The 1,4-
dihydro-2H-3,1-benzoxazin-2-ones were generally pre-
2
pared by the reaction of amino alcohols with phosgene or
3
ethylchloroformate. In addition to these stoichiometric
methods, the catalytic synthetic method of 1,4-dihydro-
2
H-3,1-benzoxazin-2-ones by the transition metal
complex-catalyzed carbonylation of amino or nitro sub-
stituted benzyl alcohols with carbon monoxide has been
developed. Up to now, it has been known that ruthenium
and palladium complexes act as a catalyst for the
1
,4-dihydro-2H-3,1-benzoxazine-2-one (2a) was formed
7
in 91% yield (entry 4). The yield of 2a decreased when
the reaction was carried out at a lower carbon monoxide
pressure and at lower reaction temperatures (80 °Cand
4
reaction, however, there is no example of the use of non-
1
20 °C, entries 1–4 and 6–7). The use of Et N and DBU
transition metals as a catalyst.
3
did not give better results than that of N-methylpyrrolidine
entries 4 and 8–9). Although the preparation of 2a by the
We have recently reported that selenium catalyzed the re-
(
action of 2-nitrostyrenes or N-(2-nitrobenzoyl)amides
reaction of 1a with carbon monoxide in the presence of
the selenium catalyst occurred, even in DMF, benzene and
acetonitrile instead of THF as the solvent, the yields of 1a
slightly decreased (entries 4 and 11–13). In the reaction,
the decrease in the amount of selenium led to the de-
5
with carbon monoxide to give indoles or 3,4-dihydro-
6
quinazolin-4-ones in moderate to good yields. In these
reactions, a reaction pathway including the formation of
nitrene (or nitrenoid) intermediate, which was generated
by the reductive deoxygenating of the nitro group by car-
bon monoxide in the presence of a selenium catalyst, was
suggested. Thus, it is expected that if the carbonylation of
the nitrene (or nitrenoid) by carbon monoxide followed by
the intramolecular addition of a hydroxy group to isocy-
anate generated in situ would smoothly occur, 1,4-dihy-
dro-2H-3,1-benzoxazin-2-ones can be prepared by the
treatment of 2-nitrobenzyl alcohols and carbon monoxide
in the presence of a catalytic amount of selenium
creased yield of 2a; however, the yield of 2a was im-9
proved by the extending the reaction time (15 h, entry 5).
To know the scope and limitation of the selenium-cata-
lyzed synthetic method of cyclic carbamates, various 2-ni-
trophenyl substituted alkanols were treated with carbon
monoxide in the presence of a catalytic amount of seleni-
um in THF solution (Table 2).10 When the 3-methyl-, 4-
methyl-, 5-methyl-, 4-methoxy-, and 4-chloro-2-nitro-
benzylalcohols were allowed to react with carbon monox-
ide, the 1,4-dihydro-2H-3,1-benzoxazin-2-ones were
obtained in 78–92 yields, respectively (entries 2–6). In the
case of (2-nitrophenyl)-1,2-ethanediol, a six-membered
cyclic carbamate, was preferentially formed (entry 7). For
(
Scheme 1). In this paper, we show a new approach for the
synthesis of 1,4-dihydro-2H-3,1-benzoxazin-2-ones by
SYNLETT 2004, No. 5, pp 0886–0888
0
2.
0
4.
2
0
0
4
Advanced online publication: 24.02.2004
DOI: 10.1055/s-2004-820018; Art ID: U29403ST
2
-nitrophenylethyl alcohol, the yield of the carbamate
©
Georg Thieme Verlag Stuttgart · New York

LETTER
A New Synthetic Method of 1,4-Dihydro-2H-3,1-benzoxazin-2-ones
887
Table 1 Reaction of 2-Nitrobenzyl Alcohol with Carbon Monoxide
Table 2 Synthesis of Cyclic Carbamatesa
in the Presence of a Catalytic Amount of Seleniuma
Entry Substrate
1
Product
Yield
(%)
b
OH
Se (Cat.)
O
+
CO
base
NO2
91
N
H
O
OH
NO2
O
O
solvent
1
a
2a
N
H
O
Entry Base
1
Solvent CO
Temp
(°C)
Yield
(%)
2
a
b
(
atm)
2
78
5
150
54
N-CH3
OH
NO2
N
H
O
O
2
10
20
30
30
30
30
30
30
30
30
150
150
150
150
120
80
82
2
2
2
b
c
3
87
3
4
91
88
92
4
91 (85)
88
OH
NO2
5c
6
N
H
O
55
7
Trace
67
OH
NO2
O
8
9
0
1
Et N
150
150
150
150
3
N
H
O
O
DBU
77
d
1
1
K CO3
0
2
5
6
7
MeO
MeO
OH
NO2
DMF
82
N-CH3
N
H
O
1
2
3
2
CH CN 30
150
150
90
50
2e
3
81
75
1
benzene 30
Cl
Cl
OH
NO2
O
a
-Nitrobenzyl alcohol (0.5 mmol), Se (0.1 mmol), base (5.0 mmol)
and solvent (5 mL) for 5 h.
GC yield based on 2-nitrobenzyl alcohol. The number in parenthe-
sis indicates the isolated yield.
N
H
O
b
2
f
c
Se (0.02 mmol) was used, 15 h.
OH
OH
O
OH
OH
slightly decreased due to the formation of the reduction
product, 2-aminophenylethyl alcohol, as a by-product
NO2
N
H
O
(
entry 8).
2
2
g
We have previously found a convenient preparation meth-
od of carbonyl selenide (SeCO), which involved the acid-
catalyzed decomposition of secondary amine salts of sele-
nocarbamates generated by the reaction of elemental sele-
nium with carbon monoxide and secondary amine.11 It
was then proposed that the reaction starts with the deoxy-
genation of the nitro group with SeCO prepared from
elemental selenium and carbon monoxide forming the
corresponding short-lived nitrene or nitrenoid. The carbo-
nylation of the nitren intermediate by carbon monoxide
formed isocyanate and subsequent attacked of the hy-
droxy group to isocyanate to form the cyclic carbamate.
8
66
O
NO2
N
H
O
h
a
Substrate (0.5 mmol), Se (0.1 mmol), CO (30 atm), N-methypyrro-
lidine (5 mmol) and THF (5 mL) at 150 °C for 5 h.
b
GC yield based on substrate.
In summary, we succeeded in the synthesis of 1,4-dihy-
dro-2H-3,1-benzoxazine-2-ones by the reaction of o-nitro
Acknowledgment
substituted benzyl alcohols with carbon monoxide using This work was financially supported in part by a Grant-in-Aid for
Science Research on Priority Areas (C) (No. 12650840) from the
selenium as a catalyst. Further studies on the synthetic
Ministry of Education, Culture, Sports, Science and Technology,
Japan.
application and mechanism of the reaction are now in
progress.
Synlett 2004, No. 5, 886–888 © Thieme Stuttgart · New York

8
88
Y. Nishiyama et al.
LETTER
References
(10) A Typical Procedure is as follows: In a 50 mL stainless
steel autoclave were placed o-nitrobenzyl alcohol (77 mg,
.5 mmol), selenium (8 mg, 0.1 mmol), N-methylpyrrodine
425mg, 5 mmol), THF (5 mL) and a magnetic stirring bar.
The mixture was stirred under pressurized carbon monoxide
30 atm) at 140 °C for 5 h. After the evacuation of the excess
(
1) (a) Consonni, R.; Croce, P. D.; Ferraccioli, R.; La Rosa, C.
J. Chem. Soc., Perkin Trans. 1 1996, 1809. (b) Ohno, M.;
Sato, H.; Eguchi, S. Synlett 1999, 207.
0
(
(2) Testa, E.; Fontanella, L. Farmaco, Ed. Sci. 1966, 549.
(3) Ohno, M.; Sato, H.; Eguchi, S. Synlett 1999, 207.
(4) (a) Cenini, S.; Console, S.; Crotti, C.; Tollari, S. J.
Organomet. Chem. 1993, 451, 157. (b) Braunstein, P.;
Kervennal, J.; Richert, J. L. Angew. Chem., Int. Ed. Engl.
(
carbon monoxide at r.t., the deposited selenium was filtered
off; the solution was then extracted with diisopropyl ether
(
30 mL × 3). The organic layer was dried over MgSO and
4
the solvent was evaporated in vacuo. The residual solid was
1985, 24, 768. (c) Braunstein, P.; Devenish, R.; Gallezot, P.;
recrystallized from CH Cl –C H to give 1,4-dihydro-2H-
2
2
6
14
Heaton, B. T.; Humphreys, C. J.; Kervennal, J.; Mulley, S.;
Ries, M. Angew. Chem., Int. Ed. Engl. 1988, 27, 927.
5) Nishiyama, Y.; Maema, R.; Ohno, K.; Hirose, M.; Sonoda,
N. Tetrahedron Lett. 1999, 40, 5717.
6) Nishiyama, Y.; Hirose, M.; Kitagaito, W.; Sonoda, N.
Tetrahedron Lett. 2002, 43, 1855.
7) Recently, Gang et al. reported the synthesis of
benzoxazolinone by the selenium-catalyzed carbonylation
of o-nitrophenol with carbon monoxide. See: Gang, L.;
Junzhu, C.; Shiwei, L. Cuihua Xueban 2003, 24, 5.
8) We also showed the selenium catalyzed the synthetic
method of cyclic ureas, urethanes and quinazolinedione by
the carbonylation of aromatic amines with carbon monoxide.
See: Yoshida, T.; Kambe, N.; Murai, S.; Sonoda, N. Bull.
Chem. Soc. Jpn. 1987, 60, 1793.
1
,3-benzoxazine-2-one in 85% yield.
1
Compound 2g: H NMR (d -DMSO): d = 2.50 (s, 1 H), 3.34
6
(
(
(
(br s, 1 H), 5.17 (t, J = 5.2 Hz, 1 H), 5.35 (t, J = 4.0 Hz, 1 H),
6
.83 (t, J = 8.0 Hz, 1 H), 6.98 (t, J = 8.0 Hz, 1 H), 7.21 (q,
13
J = 8.0 Hz, 2 H), 10.41 (s, 1 H). C NMR: d = 63.8, 79.5,
1
7
1
13.4, 118.6, 121.8, 124.9, 128.4, 136.0, 150.5. IR: 659.6,
53.5, 1058.8, 1087.6, 1263.6, 1291.8, 1413.6, 1692.5,
686.7, 2947.0, 3090.8, 3154.1, 3235.4, 3333.2 cm .
–1
1
Compound 2h: H NMR (d -DMSO): d = 3.21 (t, J = 4.8 Hz,
2
6
H), 4.52 (t, J = 4.8 Hz, 2 H), 6.97 (d, J = 7.6 Hz, 1 H), 7.00
(
(
(
t, J = 7.6 Hz, 1 H), 7.09 (d, J = 7.6 Hz, 1 H), 7.17 (t, J = 7.6
13
Hz, 1 H), 8.83 (s, 1 H). C NMR: d = 34.5, 68.1, 119.4,
1
7
3
23.1, 126.2, 127.7, 130.3, 136.0, 157.2. IR: 679.7, 741.9,
56.5, 1058.4, 1090.9, 1277.5, 1339.7, 1420.6, 1682.3,
–1
102.0, 3238.0 cm .
9) When 1a was treated with carbon monoxide and water (5
equiv) in the presence of a catalytic amount of selenium at
(
11) Kondo, K.; Yokoyama, S.; Miyoshi, N.; Murai, S.; Sonoda,
N. Angew. Chem., Int. Ed. Engl. 1979, 18, 691.
150 °C for 5 h, 2a was not obtained and 2-aminobenzyl
alcohol was formed in 87% yield.
Synlett 2004, No. 5, 886–888 © Thieme Stuttgart · New York