A simple synthesis of 4H-1,3-benzodioxin-2-one derivatives by iodocyclization of t-butyl o-vinylphenyl carbonate derivatives

Article abstract of DOI:10.1246/bcsj.79.489

The first general method for the synthesis of 4H-1,3-benzodioxin-2-one derivatives has been developed. Treatment of t-butyl 2-vinylphenyl carbonates with iodine in the presence of sodium hydrogencarbonate gave 4-iodomethyl-4H-1,3-benzodioxin-2-one derivat

Full text of DOI:10.1246/bcsj.79.489

Short Articles
Bull. Chem. Soc. Jpn. Vol. 79, No. 3, 489–491 (2006)
489
R2 R1
R2
R1
I
R3
R4
R3
R4
A Simple Synthesis of 4H-1,3-
Benzodioxin-2-one Derivatives by
Iodocyclization of t-Butyl o-Vinyl-
phenyl Carbonate Derivatives
I2, NaHCO3
O
MeCN, 0 °C
OCO2But
O
O
1
2a 52%
2b 83%
2c 62%
2d 43%
2e 91%
2f 70%
a R1 = Me, R2 = R3 = R4 = H
b R1 = Ph, R2 = R3 = R4 = H
c R1 = Ph, R2 = R4 = H, R3 = Me
d R1 = R4 = Me, R2 = R3 = H
e R1 = Ph, R2−R3 = benzo, R4 = H
ꢀ
Kazuna Miyamoto, Osamu Morikawa,
Kazuhiro Kobayashi, Daizo Nakamura,
f
R1 = Ph, R2 = R3 = H, R4 = OMe
and Hisatoshi Konishi
R2
R1
Me
O
R3
R4
n-Bu3SnH
Department of Materials Science, Faculty of Engineering,
Tottori University, 4-101 Koyama-minami, Tottori 680-8552
C6H6, rt
O
O
Received September 20, 2005; E-mail: kkoba@chem.tottori-u.
ac.jp
3a 95%
3b 91%
3c 84%
3d 98%
3e 81%
The first general method for the synthesis of 4H-1,3-
benzodioxin-2-one derivatives has been developed. Treat-
ment of t-butyl 2-vinylphenyl carbonates with iodine in the
presence of sodium hydrogencarbonate gave 4-iodomethyl-
4H-1,3-benzodioxin-2-one derivatives in moderate to good
yields. These iodides were reduced with tributyltin hydride
to give the corresponding 4-methyl-4H-1,3-benzodioxin-2-
one derivatives.
Scheme 1.
room temperature and that the corresponding 4-methyl-4H-
1,3-benzodioxin-2-one derivatives 3a–3e were obtained in
good to excellent yields, as shown in Scheme 1. However,
when 2f was used, this compound was unstable under the
above reaction conditions and no desired product was detected;
the corresponding o-vinylphenol derivative arising from decar-
boxylation was the only product, produced almost quantita-
tively.
Surprisingly, there have been few reports on the synthesis
of 4H-1,3-benzodioxin-2-one derivatives. The reaction of 2-
hydroxybenzyl alcohol derivatives with phosgene has been
used to prepare this class of molecules.1 This method, how-
ever, suffers from low yields and limited generality; therefore,
their utility has not been examined so far. 4H-1,3-Benzodi-
oxin-2-one derivatives, however, are of potential interest from
a biological point of view, because their 1-nitrogen analogues,
1,4-dihydrobenz[d][1,3]oxazin-2-one derivatives, have been
reported to exhibit a variety of biological activities.2 We, there-
fore, decided to develop a simple and general method for the
preparation of 4H-1,3-benzodioxin-2-one derivatives. In the
present paper, we wish to describe the results of our work,
which provide the first general access to this class of molecules.
The method is based on the iodocyclization3 of t-butyl o-vinyl-
phenyl carbonates 1, giving 4-iodomethyl-4H-1,3-benzodiox-
in-2-one derivatives 2.
The method we have developed for the construction of the
4H-1,3-benzodioxin-2-one skeleton is outlined in Scheme 1.
Thus, t-butyl o-vinylphenyl carbonates 1, which were easily
prepared by the t-butoxycarbonylation of readily available o-
vinylphenols4 with di-t-butyl dicarbonate using sodium hydride
as a base, were treated with iodine in the presence of sodium
hydrogencarbonate in acetonitrile at 0 ꢁC to give 4-iodometh-
yl-4H-1,3-benzodioxin-2-one derivatives 2 in moderate to good
yields. These products are somewhat unstable, but storable at
refrigerator temperature for a few weeks.
The results reported above demonstrate that 4H-1,3-benzo-
dioxin-2-one derivatives can be easily prepared from readily
available 2-vinylphenol derivatives. Work on further applica-
tions utilizing this type of cyclization for the preparation of
related heterocycles is now in progress in our laboratory.
Experimental
Starting Materials. 2-(1-Methylethenyl)phenol,4a 2-(1-phen-
ylethenyl)phenol,4b 4-methyl-2-(1-phenylethenyl)phenol,4c 1-(1-
phenylethenyl)naphthalen-2-ol,4c and 5-methoxy-2-(1-phenyleth-
enyl)phenol4b were prepared by the appropriate literature meth-
ods. All other chemicals used in this study were commercially
available.
t-Butyl 2-(1-Methylethenyl)phenyl Carbonate (1a). To a
stirred suspension of NaH (0.19 g, 60% in oil, 4.7 mmol) in
THF (5 mL) at 0 ꢁC was added dropwise a solution of 2-(1-meth-
ylethenyl)phenol4a (0.25 g, 1.9 mmol) in THF (2 mL). After 5 min,
di-t-butyl dicarbonate (1.0 g, 4.7 mmol) was added and the mix-
ture was stirred for 1 h at the same temperature. The resulting re-
action mixture was treated with aqueous saturated NH4Cl (15 mL)
and the organic materials were extracted with Et2O three times
(10 mL each). The combined extracts were washed with brine
and dried over anhydrous Na2SO4. The solvent and excess di-t-
butyl dicarbonate were removed under reduced pressure. The res-
idue was purified by column chromatography on silica gel to give
1a (0.38 g, 86%); a colorless liquid; Rf 0.64 (1:3 AcOEt–hexane);
IR (neat) 1759 and 1638 cmꢂ1 1H NMR (500 MHz, CDCl3) ꢀ
;
It was found that hydrogen displaced the iodine atom of 2a–
2e cleanly on treatment with tributyltin hydride in benzene at
1.52 (9H, s), 2.08 (3H, s), 5.07 (1H, d, J ¼ 1:0 Hz), 5.20 (1H, d,
J ¼ 1:0 Hz), 7.10 (1H, d, J ¼ 8:2 Hz), 7.20 (1H, td, J ¼ 7:3 and
Published on the web March 8, 2006; DOI 10.1246/bcsj.79.489

490 Bull. Chem. Soc. Jpn. Vol. 79, No. 3 (2006)
Ó 2006 The Chemical Society of Japan
1.4 Hz), and 7.24–7.29 (2H, m). Found: C, 71.55; H, 8.00%. Calcd
for C14H18O3: C, 71.77; H, 7.74%.
taining NaHCO3 (0.23 g, 2.7 mmol) at 0 ꢁC was added iodine
(0.69 g, 2.7 mmol) portionwise. After stirring for 30 min, 10%
aqueous Na2S2O3 was added until the color of iodine disappeared,
and the mixture was extracted with CH2Cl2 three times (10 mL
each). The combined extracts were washed with aqueous saturated
NaHCO3 and brine, dried over anhydrous K2CO3, and evaporated.
The residue was purified by column chromatography on silica gel
(6:1 hexane–AcOEt) to give 2a (0.14 g, 52%); a pale-yellow solid;
t-Butyl 2-(1-Phenylethenyl)phenyl Carbonate (1b): Prepar-
ed from 2-(1-phenylethenyl)phenol4b in a manner similar to that
described for the preparation of 1a in 81% yield; a colorless oil;
Rf 0.47 (1:10 AcOEt–hexane); IR (neat) 1755 cmꢂ1 1H NMR
;
(500 MHz, CDCl3) ꢀ 1.34 (9H, s), 5.36 (1H, d, J ¼ 0:9 Hz), 5.70
(1H, d, J ¼ 0:9 Hz), 7.16 (1H, dd, J ¼ 8:2 and 1.3 Hz), 7.23–7.32
(7H, m), and 7.36 (1H, ddd, J ¼ 8:2, 7.3, and 1.8 Hz). Found: C,
77.36; H, 6.87%. Calcd for C19H20O3: C, 77.00; H, 6.80%.
t-Butyl 4-Methyl-2-(1-phenylethenyl)phenyl Carbonate (1c):
Prepared from 4-methyl-2-(1-phenylethenyl)phenol4c as describ-
ed for preparation of 1a in 89% yield; a colorless oil; Rf 0.69
mp 96–97 ꢁC (hexane–CH2Cl2); IR (KBr disk) 1761 cmꢂ1
;
1H NMR (500 MHz, CDCl3) ꢀ 1.95 (3H, s), 3.61 (1H, d, J ¼
11:5 Hz), 3.64 (1H, d, J ¼ 11:5 Hz), 7.13 (1H, dd, J ¼ 7:8 and
1.4 Hz), 7.17 (1H, dd, J ¼ 7:8 and 1.4 Hz), 7.26 (1H, td, J ¼ 7:8
and 1.4 Hz), and 7.41 (1H, dt, J ¼ 7:8 and 1.4 Hz); MS m=z 304
(Mþ, 0.28) and 260 (100). Found: C, 39.48; H, 2.99%. Calcd
for C10H9IO3: C, 39.50; H, 2.98%.
(1:3 AcOEt–hexane); IR (neat) 1755 cmꢂ1 1H NMR (500 MHz,
;
CDCl3) ꢀ 1.33 (9H, s), 2.34 (3H, s), 5.33 (1H, d, J ¼ 0:9 Hz), 5.67
(1H, d, J ¼ 0:9 Hz), 7.03 (1H, d, J ¼ 7:8 Hz), 7.10 (1H, d, J ¼
1:8 Hz), 7.15 (1H, dd, J ¼ 7:8 and 1.8 Hz), and 7.23–7.32 (5H, m).
Found: C, 77.37; H, 7.36%. Calcd for C20H22O3: C, 77.39; H,
7.14%.
4-Iodomethyl-4-phenyl-4H-1,3-benzodioxin-2-one (2b). The
preparation of this compound was conducted as described for the
preparation of 1a (reaction time: 3 h). After treatment of the reac-
tion mixture with 10% aqueous Na2S2O3, MeCN was evaporated.
The resulting precipitate was collected by filtration and recrystal-
lized from hexane–CH2Cl2 to give 2b: a white solid; mp 124–127
2-(1-Hydroxy-1-methylethyl)-5-methylphenol:
Prepared
from 1-(2-hydroxy-4-methylphenyl)ethanone and MeMgBr in
92% yield; a white solid; mp 63–64 ꢁC (hexane–Et2O); IR (KBr
ꢁC (hexane–CH2Cl2); IR (KBr disk) 1771 cmꢂ1 1H NMR (500
;
disk) 3393 and 1618 cmꢂ1
;
1H NMR (500 MHz, CDCl3) ꢀ 1.66
MHz, CDCl3) ꢀ 3.89 (1H, d, J ¼ 11:9 Hz), 3.98 (1H, d, J ¼ 11:9
Hz), 7.15 (1H, d, J ¼ 8:2 Hz), 7.31–7.38 (7H, m), and 7.47 (1H,
ddd, J ¼ 9:2, 8.2, and 2.8 Hz); MS m=z 366 (Mþ, 2.3), 322 (11),
and 195 (100). Found: C, 48.90; H, 3.11%. Calcd for C15H11IO3:
C, 49.20; H, 3.03%.
(6H, s), 2.19 (1H, s), 2.28 (3H, s), 6.64 (1H, dd, J ¼ 7:8 and
0.9 Hz), 6.71 (1H, s), 6.96 (1H, d, J ¼ 7:8 Hz), and 8.79 (1H, s).
Found: C, 72.14; H, 8.53%. Calcd for C10H14O2: C, 72.26; H,
8.49%.
5-Methyl-2-(1-methylethenyl)phenol:4d Prepared by thermal
dehydration of 2-(1-hydroxy-1-methylethyl)-5-methylphenol
(160 ꢁC, neat) in 73% yield; a colorless liquid; Rf 0.61 (3:1 hex-
4-Iodomethyl-6-methyl-4-phenyl-4H-1,3-benzodioxin-2-one
(2c): Prepared from 1c in a manner similar to that described for
the preparation of 2b; a white solid; mp 127–130 ꢁC (hexane–
1
1
ane–AcOEt); IR (neat) 3512 and 1631 cmꢂ1; H NMR (500 MHz,
CH2Cl2); IR (KBr disk) 1773 cmꢂ1; H NMR (500 MHz, CDCl3)
CDCl3) ꢀ 2.10 (3H, t, J ¼ 0:9 Hz), 2.30 (3H, s), 5.12 (1H, quint,
J ¼ 0:9 Hz), 5.37 (1H, quint, J ¼ 0:9 Hz), 5.65 (1H, s), 6.71 (1H,
dd, J ¼ 7:8 and 0.9 Hz), 6.76 (1H, s), and 7.02 (1H, d, J ¼ 7:8 Hz).
t-Butyl 5-Methyl-2-(1-methylethenyl)phenyl Carbonate
ꢀ 2.45 (3H, s), 3.87 (1H, d, J ¼ 11:9 Hz), 3.97 (1H, d, J ¼ 11:9
Hz), 7.02 (1H, d, J ¼ 8:2 Hz), 7.10 (1H, d, J ¼ 1:4 Hz), 7.25 (1H,
dd, J ¼ 8:2 and 1.4 Hz), and 7.32–7.38 (5H, m); MS m=z 336
[ðM ꢂ CO2Þþ, 5.9] and 209 (100). Found: C, 50.39; H, 3.51%.
Calcd for C16H13IO3: C, 50.55; H, 3.45%.
4-Iodomethyl-4,7-dimethyl-4H-1,3-benzodioxin-2-one (2d):
Prepared from 1d as described for the preparation of 2b (reaction
time: 30 min); a white solid; mp 121–123 ꢁC (hexane–CH2Cl2); IR
(KBr disk) 1755 and 1634 cmꢂ1 1H NMR (500 MHz, CDCl3) ꢀ
;
1.92 (3H, s), 2.39 (3H, s), 3.58 (1H, d, J ¼ 11:0 Hz), 3.62 (1H, d,
J ¼ 11:0 Hz), 6.93 (1H, s), and 7.02–7.07 (2H, s); MS m=z 318
(Mþ, 0.50), 274 (6.2), and 147 (100). Found: C, 41.34; H, 3.50%.
Calcd for C11H11IO3: C, 41.53; H, 3.49%.
1-Iodomethyl-1-phenyl-1H-2,4-naphtho[2,1-d]dioxin-3-one
(2e): Prepared from 1e as described for the preparation of 2b
(reaction time: 1 day); a white solid; mp 103–105 ꢁC (hexane–
CH2Cl2); IR (KBr disk) 1776 and 1630 cmꢂ1; 1H NMR (500 MHz,
CDCl3) ꢀ 4.53 (1H, d, J ¼ 11:5 Hz), 4.65 (1H, d, J ¼ 11:5 Hz),
7.30–7.40 (6H, m), 7.42–7.48 (3H, m), 7.89 (1H, d, J ¼ 8:2 Hz),
and 7.96 (1H, d, J ¼ 8:7 Hz); MS m=z 372 [ðM ꢂ CO2Þþ, 20]
and 245 (100). Found: C, 55.10; H, 3.25%. Calcd for C19H13IO3:
C, 54.83; H, 3.15%.
4-Iodomethyl-7-methoxy-4-phenyl-4H-1,3-benzodioxin-2-one
(2f): Prepared from 1f as described for the preparation of 2b;
a white solid; mp 85–88 ꢁC; IR (KBr disk) 1784 and 1626 cmꢂ1
;
1H NMR (500 MHz, CDCl3) ꢀ 3.846 (3H, s), 3.848 (1H, d, J ¼
11:9 Hz), 3.97 (1H, d, J ¼ 11:9 Hz), 6.66 (1H, d, J ¼ 2:3 Hz),
6.88 (1H, dd, J ¼ 8:2 and 2.3 Hz), 7.21 (1H, d, J ¼ 8:2 Hz), and
7.28–7.37 (5H, m); MS m=z 396 (Mþ, 0.21), 352 (20), and 225
(100). Found: C, 48.47; H, 3.37%. Calcd for C16H13IO4: C,
48.51; H, 3.31%.
(1d):
described for the preparation of 1a in 89% yield; Rf 0.71 (3:1
Prepared from 5-methyl-2-(1-methylethenyl)phenol as
1
hexane–AcOEt); IR (neat) 1759, 1638, and 1620 cmꢂ1; H NMR
(500 MHz, CDCl3) ꢀ 1.52 (9H, s), 2.06 (3H, s), 2.34 (3H, s), 5.05
(1H, d, J ¼ 0:9 Hz), 5.16 (1H, d, J ¼ 0:9 Hz), 6.92 (1H, s), 7.00
(1H, d, J ¼ 7:8 Hz), and 7.16 (1H, d, J ¼ 7:8 Hz). Found: C,
72.88; H, 8.19%. Calcd for C15H20O3: C, 72.55; H, 8.12%.
t-Butyl 1-(1-Phenylethenyl)naphthalen-2-yl Carbonate (1e):
Prepared from 1-(1-phenylethenyl)naphthalen-2-ol4c as described
for the preparation of 1a in 84% yield; a white solid; mp
69–70 ꢁC (hexane–Et2O); IR (KBr disk) 1753 and 1618 cmꢂ1
;
1H NMR (500 MHz, CDCl3) ꢀ 1.39 (9H, s), 5.36 (1H, d, J ¼
1:4 Hz), 6.15 (1H, d, J ¼ 1:4 Hz), 7.20–7.27 (3H, m), 7.30–7.36
(3H, m), 7.41 (1H, ddd, J ¼ 7:8, 7.3, and 1.4 Hz), 7.46 (1H, ddd,
J ¼ 7:8, 7.3, and 1.4 Hz), and 7.85–7.89 (3H, m). Found: C,
79.70; H, 6.50%. Calcd for C23H22O3: C, 79.74; H, 6.40%.
t-Butyl 2-(1-Phenylethenyl)-5-methoxyphenyl Carbonate
(1f): Prepared from 5-methoxy-2-(1-phenylethenyl)phenol4b as
described for the preparation of 1a in 87% yield; a colorless oil;
Rf 0.76 (1:3 AcOEt–hexane); IR (neat) 1759 and 1618 cmꢂ1
;
1H NMR (500 MHz, CDCl3) ꢀ 1.35 (9H, s), 3.82 (3H, s), 5.32 (1H,
d, J ¼ 1:4 Hz), 5.63 (1H, d, J ¼ 1:4 Hz), 6.71 (1H, d, J ¼ 2:3 Hz),
6.79 (1H, dd, J ¼ 8:2 and 2.3 Hz), 7.19 (1H, d, J ¼ 8:2 Hz), and
7.24–7.32 (5H, m). Found: C, 73.54; H, 6.84%. Calcd for
C20H22O4: C, 73.60; H, 6.79%.
4-Iodomethyl-4-methyl-4H-1,3-benzodioxin-2-one (2a). To
a stirred solution of 1a (0.21 g, 0.90 mmol) in MeCN (9 mL) con-

K. Kobayashi et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 3 (2006)
491
4,4-Dimethyl-4H-1,3-benzodioxin-2-one (3a). After a mix-
ture of 2a (0.18 g, 0.59 mmol) and n-Bu3SnH (0.34 g, 1.2 mmol)
in benzene (4 mL) was stirred at room temperature for 2 h, the sol-
vent was evaporated and the residue was purified by column chro-
matography on silica gel to give 3a (0.10 g, 95%); a colorless oil;
Rf 0.40 (1:4 AcOEt–hexane). IR and 1H NMR data of this product
were identical to those reported previously.1c
for Scientific Research (C) No. 15550092 from Japan Society
for the Promotion of Science.
References
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a) D. Berney, P. Deslongchamps, Can. J. Chem. 1969, 47,
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4-Methyl-4-phenyl-4H-1,3-benzodioxin-2-one (3b). Com-
pound 2b was treated with n-Bu3SnH in benzene in a manner sim-
ilar to that described above for the preparation of 3a. After evap-
oration of the solvent, the residual solid was recrystallized from
hexane–CH2Cl2 to give 3b; a white solid; mp 113–114 ꢁC; IR
2
L. Bernardi, S. Coda, A. Bonsignori, L. Pegrassi, G. K.
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1
(KBr disk) 1771 cmꢂ1; H NMR (500 MHz, CDCl3) ꢀ 2.08 (3H,
s), 7.13 (1H, d, J ¼ 8:7 Hz), 7.26–7.37 (7H, m), and 7.42 (1H,
ddd, J ¼ 7:8, 6.4, and 2.3 Hz); MS m=z 196 [ðM ꢂ CO2Þþ, 100].
Found: C, 74.79; H, 5.12%. Calcd for C15H12O3: C, 74.99; H,
5.03%.
4,6-Dimethyl-4-phenyl-4H-1,3-benzodioxin-2-one (3c): Pre-
pared as described for the preparation of 3b; a white solid;
mp 116–118 ꢁC (hexane–CH2Cl2); IR (KBr disk) 1771 cmꢂ1
;
1H NMR (500 MHz, CDCl3) ꢀ 2.06 (3H, s), 2.40 (3H, s), 7.01
(1H, d, J ¼ 8:2 Hz), 7.07 (1H, d, J ¼ 1:4 Hz), 7.20 (1H, dd, J ¼
8:2 and 1.4 Hz), and 7.28–7.37 (5H, m); MS m=z 210 [ðM ꢂ
CO2Þþ, 58] and 209 (100). Found: C, 75.43; H, 5.60%. Calcd
for C16H14O3: C, 75.57; H, 5.55%.
4,4,7-Trimethyl-4H-1,3-benzodioxin-2-one (3d): Prepared
as described for the preparation of 3b; a white solid; mp 62 ꢁC
(hexane–CH2Cl2); IR (KBr disk) 1774 cmꢂ1; 1H NMR (500 MHz,
CDCl3) ꢀ 1.73 (6H, s), 2.37 (3H, s), 6.91 (1H, s), 7.01 (1H, d,
J ¼ 7:8 Hz), and 7.06 (1H, d, J ¼ 7:8 Hz); MS m=z 192 (Mþ,
0.42) and 148 (100). Found: C, 68.50; H, 6.31%. Calcd for
C11H12O3: C, 68.74; H, 6.29%.
1-Methyl-1-phenyl-1H-2,4-naphtho[2,1-d]dioxin-3-one (3e):
Prepared as described for the preparation of 3b (reaction time: 2
days); a white solid; mp 106–108 ꢁC (hexane–CH2Cl2); IR (KBr
disk) 1774 and 1630 cmꢂ1 1H NMR (500 MHz, CDCl3) ꢀ 2.41
;
3
The formation of 4-iodomethyl-1,3-dioxan-2-ones by iodo-
cyclization of t-butyl homoallyl carbonates has been reported pre-
viously: P. A. Bartlett, J. D. Meadows, E. G. Brown, A. Morimoto,
K. K. Jernstedt, J. Org. Chem. 1982, 47, 4013; See also a recent
application: J. Wiseman, F. E. McDonald, D. C. Liotta, Org. Lett.
2005, 7, 3155.
(3H, s), 7.24–7.29 (2H, m), 7.31 (1H, d, J ¼ 9:2 Hz), 7.36–7.41
(4H, m), 7.45–7.48 (2H, m), 7.84 (1H, d, J ¼ 8:2 Hz), and 7.90
(1H, d, J ¼ 8:7 Hz); MS m=z 246 [ðM ꢂ CO2Þþ, 100]. Found:
C, 78.54; H, 5.00%. Calcd for C19H14O3: C, 78.61; H, 4.86%.
4
a) B. A. M. Oude-Alink, A. W. K. Chan, C. D. Gutsche,
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We wish to thank Mrs. Miyuki Tanmatsu of this department
for determining MS spectra and performing combustion analy-
ses. This research was partially supported by a Grant-in-Aid