Palladium-catalyzed carbonylation of o-iodoanilines for synthesis of isatoic anhydrides

Article abstract of DOI:10.1021/jo500417u

A novel palladium-catalyzed oxidative double carbonylation of o-iodoanilines for the synthesis of isatoic anhydrides has been developed. The reaction employs readily available o-iodoanilines as the starting materials and proceeds under mild conditions. For extension, palladium-catalyzed oxidative carbonylation of anthranilic acids was developed for the synthesis of substituted isatoic anhydrides in high to excellent yields.

Full text of DOI:10.1021/jo500417u

Note
pubs.acs.org/joc
Palladium-Catalyzed Carbonylation of o‑Iodoanilines for Synthesis of
Isatoic Anhydrides
Sha Gao, Ming Chen, Mi-Na Zhao, Wei Du, Zhi-Hui Ren, Yao-Yu Wang, and Zheng-Hui Guan*
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry and
Materials Science, Northwest University, Xi’an 710069, P. R. China
*
S Supporting Information
ABSTRACT: A novel palladium-catalyzed oxidative double carbonylation of o-iodoanilines for the synthesis of isatoic
anhydrides has been developed. The reaction employs readily available o-iodoanilines as the starting materials and proceeds
under mild conditions. For extension, palladium-catalyzed oxidative carbonylation of anthranilic acids was developed for the
synthesis of substituted isatoic anhydrides in high to excellent yields.
ver the past decades, transition-metal-catalyzed carbon-
ylations with CO as a C1 source have been demonstrated
isatoic anhydrides under mild conditions. However, the
intrinsic alkyl group on the nitrogen atom was hardly
removable to produce the synthetically useful N-unsubstituted
isatoic anhydrides. We hypothesized that palladium-catalyzed
double carbonylation of readily available o-iodoanilines may be
a straightforward route to synthesize of N-unsubstituted isatoic
anhydrides. In this paper, we have developed a novel palladium-
catalyzed oxidative double carbonylation of o-iodoanilines for
the synthesis of N-unsubstituted isatoic anhydrides.
O
as one of the most powerful tools for the synthesis of various of
1
carbonyl compounds. Especially, palladium-catalyzed carbon-
ylation of aryl iodides or aryl bromides has been widely applied
to synthesize aromatic esters, amides, and ketones in both
2
academic and industrial communities. Palladium-catalyzed
carbonylation of challenging substrates such as aryl chlorides
or aryl triflates has also been achieved by using electron-rich
3
and bulky phosphine ligands. Recently, carbonylation with a
We began our study by investigating the palladium-catalyzed
oxidative double carbonylation of o-iodoaniline 1a in the
subsequent intramolecular cyclization reaction has been shown
to be an efficient process for the straightforward synthesis of
presence of CuCl
anhydride 3a was obtained in 21% yield under 3 atm of CO/O
(2:1) at 100 °C (Table 1, entry 1). However, no desired
product was observed in the presence of CuBr , and 2-methyl-
H-benzo[d][1, 3]oxazin-4-one 4 was obtained in 14% yield
when Cu(OAc) was used as the oxidant (Table 1, entry 3).
2 2 3 3
and K CO in CH CN. The desired isatoic
4
heterocycles. The pioneering work of palladium-catalyzed
2
carbonylation of o-iodoanilines, o-iodophenols, or o-iodothio-
phenols with a series of suitable coupling partners has been
developed for the synthesis of valuable heterocycles by Alper
2
4
5
and co-workers. The group of Wu and Beller has developed a
2
Screening of various bases and solvents revealed that K PO
series of elegant palladium-catalyzed carbonylation of o-
bromobenzaldehydes, o-hydroxyacetophenones, o-hydroxyben-
zaldehydes, and o-aminobenzamide with suitable coupling6
partners for the synthesis of pharmaceutical heterocycles.
However, the double carbonylation of o-iodoanilines for direct
synthesis of isatoic anhydrides, which are a class of valuable
chemicals and versatile building blocks, has not yet been
realized.
3
4
and CH CN were the best choice for this carbonylation
3
reaction (Table 1, entries 4−8). Then KI, which has been
shown to improve the efficiency of palladium-catalyzed
2c,8,9
carbonylations, was added to the reaction.
a was slightly improved to 31% (Table 1, entry 9). To
examine if the oxygen in the isatoic anhydride was coming from
The yield of
3
water in the solvent, 2.0 equiv of H O was added in the
2
reaction. However, the reaction turned messy although a similar
yield was obtained (Table 1, entry 10). Therefore, various
Conventional methods for the synthesis of substituted isatoic
anhydrides involve cyclization of anthranilic acid by highly toxic
7
dehydrating agents such as CaCl , 4 Å molecular sieves,
chloroformate or triphosgene. The reaction is limited in
2
MgSO , and Na SO , along with PivOH, which may provide
substrate scope and proceeds under harsh conditions. New
methods for the synthesis of substituted isatoic anhydrides that
are compatible with various functional groups and proceed
under mild conditions remain highly desirable. In 2012, we
developed a palladium-catalyzed carbonylation of C−H bonds
4
2
4
oxygen, were screened to improve the reaction efficiency. We
were pleased to find that the yield of isatoic anhydride 3a was
improved to 68% when KI, anhydrous CaCl , and PivOH were
2
combined to be the additives (Table 1, entry 13). Changing the
8
of N-alkyl anilines for the synthesis of isatoic anhydrides. This
reaction tolerates a wide range of functional groups and is a
practical method for the rapid synthesis of substituted N-alkyl
Received: February 20, 2014
Published: April 10, 2014
©
2014 American Chemical Society
4196
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The Journal of Organic Chemistry
Note
a
Table 1. Optimization of Conditions for Palladium-Catalyzed Oxidative Double Carbonylation of o-Iodoaniline
entry
oxidant
base
additive (equiv)
solvent
yield (%)
1
2
3
4
5
6
7
8
9
CuCl2
CuBr2
Cu(OAc)2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
K CO
CH CN
21
0
2
3
3
3
3
K CO
2
CH CN
3
b
K CO
2
CH CN
0 (14)
6
3
Cs CO
2
CH CN
3
3
t-BuOK
CH CN
25
26
24
6
3
K PO
3
CH CN
4
3
NEt3
CH CN
3
K PO
DMF
3
4
4
4
4
4
K PO
3
KI (0.2)
CH CN
31
30
35
40
68
57
58
3
10
11
12
13
14
15
16
17
18
K PO
3
KI (0.2)/H O (2.0)
CH CN
2
3
K PO
3
KI (0.2)/CaCl (2.0)
CH CN
2
3
K PO
3
KI (0.2)/PivOH (3.0)
CH CN
3
K PO
3
KI (0.2)/CaCl (2.0)/ PivOH (3.0)
CH CN
4
2
3
K PO
KI (0.2)/CaCl (2.0)/PivOH (1.0)
CH CN
3
4
4
4
4
4
2
3
K PO
3
KI (0.2)/CaCl (2.0)/PivOH (5.0)
CH CN
2
3
c
K PO
3
KI (0.2)/4 Å MS/PivOH (3.0)
CH CN
33
3
K PO
3
KI (0.2)/MgSO (2.0)/PivOH (3.0)
CH CN
41
42
4
3
K PO
3
KI (0.2)/Na SO (2.0)/PivOH (3.0)
CH CN
2
4
3
a
Reaction conditions: 1a (0.2 mmol), Pd(OAc) (5 mol %), oxidant (1.0 equiv), base (1.0 equiv), solvent (2 mL), CO/O (2:1) 3 atm, at 100 °C for
4 h. 2-Methyl-4H-benzo[d][1,3]oxazin-4-one 4 (14%) was isolated. 4 Å MS (60 mg).
2
2
b
c
2
amount of PivOH resulted in no improvement (Table 1, entries
4 and 15), and 4 Å molecular sieves, MgSO , and Na SO
4
In our previous palladium-catalyzed carbonylation of C−H
bonds of N-alkyl anilines for the synthesis of isatoic
anhydrides, we assumed that anthranilic acid should be a key
intermediate in the reaction. After a brief survey of reaction
conditions (see Supporting Information), we found that
palladium-catalyzed carbonylation of anthranilic acids pro-
ceeded smoothly to afford isatoic anhydrides in nearly
quantitative yields under slightly modified conditions (Scheme
1
4
2
8
were less effective than CaCl (Table 1, entries 16−18).
2
With the optimized reaction conditions in hand, a series of o-
1
0
iodoanilines were investigated. As shown in Table 2, this
novel double carbonylation reaction displayed high functional
group tolerance and proved to be a general method for the
preparation of isatoic anhydrides. Halogen substituents such as
fluoro, chloro, and bromo groups were tolerated under the
conditions. Isatoic anhydrides 3b and 3c were obtained in 79−
1
).
On the basis of the aforementioned results and previous
studies, a tentative mechanism for this carbonylation is
proposed in Scheme 2. First, oxidative addition of o-iodoaniline
to Pd(0) followed by insertion of carbon monoxide gives an
acylpalladium intermediate B. Then, the intermediate B is
transformed into intermediate C, assisted by K PO and
80% yields when 4-fluoro- or 4-chloro-substituted o-iodoani-
lines were used as the substrates (Table 2, entries 2 and 3). 5-
Chloro- and 4-bromo-substituted o-iodoanilines gave the
corresponding isatoic anhydrides 3d and 3e in 57% and 46%
yields, respectively. Reactions with electron-withdrawing group
substituted o-iodoanilines proceeded smoothly under the
standard conditions. For example, ester-substituted isatoic
anhydrides 3f and 3g were obtained in good yields (Table 2,
entries 6 and 7). However, strong electron-withdrawing nitrile,
acetyl and nitro substituted o-iodoanilines produced only the
corresponding isatoic anhydrides 3h−3j in 38−57% yields
respectively (Table 2, entries 8−10). In contrast to electron-
withdrawing group substituted substrates, electron-donating
group substituted o-iodoanilines were less reactive and gave
lower yields of isatoic anhydrides (Table 2, entries 11 and 12).
In these reactions, several byproducts, such as N-(2-
iodophenyl)pivalamide, 2-pivalamidobenzoic acid, and 1,3-
bis(2-iodophenyl)urea, were observed. Notably, 1-iodonaph-
thalen-2-amine 1m was tolerated under the conditions as well
to afford 1H-naphtho[2,1-d][1,3]oxazine-1,3(4H)-dione 3m in
3
4
11
PivOH. Reductive elimination of intermediate C affords
Pd(0) species and intermediate D. Metathesis of intermediate
D with PivOH provides anthranilic acid E by expulsion of
12
(
Piv) O. Meanwhile, Pd(0) is oxidized by Cu(II) to generate
2
the Pd(II)X catalyst. Subsequently, metathesis of Pd(II)X
2
2
specie and E produces the intermediate F, which undergoes
CO insertion to give intermediate G. Finally, reductive
elimination of intermediate G in the presence of K PO affords
3
4
isatoic anhydride 3 and Pd(0).
In summary, we have developed a novel palladium-catalyzed
oxidative double carbonylation of o-iodoanilines for the
synthesis of N-unsubstituted isatoic anhydrides. The reaction
employs readily available o-iodoanilines as the starting materials
and tolerates a range of functional groups. A tentative
mechanism of the reaction has been proposed. Palladium-
catalyzed oxidative carbonylation of anthranilic acids has also
been developed for the synthesis of substituted isatoic
anhydrides in high to excellent yields. The carbonylation
reactions provide straightforward routes for the synthesis of
56% yield (Table 2, entry 13). However, only 9% yield of N-
methyl isatoic anhydride was obtained when N-methyl o-
iodoaniline was used as the substrate.
4
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The Journal of Organic Chemistry
Note
a
Table 2. Scope of Palladium-Catalyzed Carbonylation of o-Iodoanilines for the Synthesis of Isatoic Anhydrides
a
Reaction conditions: 1 (0.2 mmol), Pd(OAc) (5 mol %), CuCl (1.0 equiv), K PO (1.0 equiv), KI (0.2 equiv), CaCl (2.0 equiv), PivOH (3.0
2
2
3
4
2
equiv), CO/O (2:1) 3 atm, CH CN (2 mL), at 100 °C, 24−96 h.
2
3
Scheme 1. Palladium-Catalyzed Carbonylation of Anthranilic
Acids for Synthesis of Isatoic Anhydrides
Scheme 2. Tentative Mechanism for Palladium-Catalyzed
Carbonylation of o-Iodoanilines
valuable N-unsubstituted isatoic anhydrides under mild
conditions.
EXPERIMENTAL SECTION
■
1
General Information. H NMR spectra were recorded at 400
13
MHz in DMSO-d , and C NMR spectra were recorded at 100 MHz
6
in DMSO-d . The following abbreviations are used to explain
6
multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet. All products were further characterized by HRMS (ESI-
1
13
TOF-Q); copies of their H NMR and C NMR spectra are provided
4
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The Journal of Organic Chemistry
Note
in Supporting Information. Infrared spectra were obtained by using
FT-IR spectrometer. Unless otherwise stated, all reagents and solvents
were purchased from commercial suppliers and used without further
purification. The o-iodoanilines 1a and 1d were prepared from the
146.7, 140.6, 139.3, 130.6, 117.7, 114.6, 112.4. HRMS calcd (ESI) m/z
+
for C H BrNNaO : [M + Na] 263.9267, found 263.9271. MS m/z
8
4
3
(relative intensity) 241 (48), 197 (100), 171 (25), 90 (50), 63 (80).
Methyl 2,4-Dioxo-2,4-dihydro-1H-benzo[d][1,3]oxazine-6-
1
0a
corresponding 2-nitroaniline according to the literature procedures.
Others were prepared from the iodination of the corresponding
carboxylate (3f). Yield: 68% (30.1 mg), white solid, mp 231−233
1
°C; H NMR (DMSO-d
, 400 MHz) δ 12.09 (s, 1 H), 8.37 (s, 1 H),
6
1
0b
substituted anilines in the presence of KI and H O in acetic acid.
8.23 (d, J = 8.4 Hz, 1 H), 7.23 (d, J = 8.4 Hz, 1 H), 3.87 (s, 3 H);
2
2
13
1
General Procedure for Palladium-Catalyzed Oxidative
Double Carbonylation of o-Iodoanilines for the Synthesis of
Isatoic Anhydrides. A mixture of o-iodoaniline 1 (0.2 mmol),
Pd(OAc) (5 mol %, 2.2 mg), CuCl (0.2 mmol, 26.9 mg), KI (0.04
C{ H} NMR (DMSO-d , 100 MHz) δ 164.7, 159.3, 146.8, 144.8,
6
1
36.9, 130.2, 124.4, 115.9, 110.7, 52.4. HRMS calcd (ESI) m/z for
+
C H NNaO : [M + Na] 244.0216, found 244.0221. MS m/z
10
7
5
2
2
(relative intensity) 221 (30), 177 (100), 146 (60), 119 (35), 90 (25),
63 (30).
mmol, 6.6 mg), PivOH (0.6 mmol, 61.2 mg), K PO (0.2 mmol, 42.4
3
4
mg), and CaCl (0.4 mmol, 44.4 mg) was stirred in CH CN (2 mL) at
2
3
Ethyl 2,4-Dioxo-2,4-dihydro-1H-benzo[d][1,3]oxazine-6-car-
1
00 °C under 3 atm of CO/O (2:1). After completion of the reaction
2
boxylate (3g). Yield: 70% (32.8 mg), white solid, mp 224−226 °C;
(
24−96 h), the reaction mixture was cooled to room temperature and
1
H NMR (DMSO-d , 400 MHz) δ 12.08 (s, 1 H), 8.37 (s, 1 H), 8.23
6
vented to discharge the excess CO and O . The reaction was quenched
2
(
1
d, J = 8.4 Hz, 1 H), 7.23 (d, J = 8.8 Hz, 1 H), 4.36−4.30 (m, 2 H),
with H O (10 mL) and extracted with EtOAc (3 × 10 mL). The
13
1
2
.34 (t, J = 7.2 Hz, 3 H); C{ H} NMR (DMSO-d , 100 MHz) δ
6
combined organic layers were dried over anhydrous Na SO and then
2
4
1
64.2, 159.3, 146.8, 144.7, 136.8, 130.1, 124.7, 115.9, 110.5, 61.2, 14.1.
evaporated in vacuo. The residue was purified by column
chromatography on silica gel to afford the corresponding isatoic
anhydride 3 with hexanes/EtOAc (3/1) as the eluent.
General Procedure for Palladium-Catalyzed Carbonylation
of Anthranilic Acids for the Synthesis of Isatoic Anhydrides.
Anthranilic acid 2 (0.2 mmol), Pd(OAc)2 (1 mol %, 0.4 mg),
Cu(OAc)2 (0.2 mmol, 36.3 mg), KI (0.04 mmol, 6.6 mg), and
+
HRMS calcd (ESI) m/z for C H NNaO : [M + Na] 258.0373,
11
9
5
found 258.0378. MS m/z (relative intensity) 235 (30), 191 (100), 163
40), 146 (50), 90 (25), 63 (25).
(
2
,4-Dioxo-2,4-dihydro-1H-benzo[d][1,3]oxazine-6-carboni-
1
trile (3h). Yield: 57% (21.6 mg), yellow solid, mp 254−256 °C; H
NMR (DMSO-d , 400 MHz) δ 12.18 (s, 1 H), 8.36 (s, 1 H), 8.09 (d, J
8.4 Hz, 1 H), 7.25 (d, J = 8.4 Hz, 1 H); C{ H} NMR (DMSO-d ,
6
13
1
=
6
CH CN (2 mL) were charged in a 10 mL round-bottom flask. A
3
1
1
2
1
00 MHz) δ 158.5, 146.6, 144.6, 139.4, 133.8, 117.7, 116.6, 111.6,
balloon filled with CO/O (3:1) was connected to the flask. Then, the
+
2
05.7. HRMS calcd (ESI) m/z for C H N NaO : [M + Na]
9
4
2
3
flask was evacuated and backfilled (3 times, balloon) and stirred at 60
11.0114, found 211.0114. MS m/z (relative intensity) 188 (35),
44 (100), 117 (70), 89 (25), 62 (25).
°
C. When the reaction was completed (detected by TLC), the mixture
was cooled to room temperature and vented to discharge the excess
CO and O . The reaction was quenched with H O (10 mL) and
6
-Acetyl-1H-benzo[d][1,3]oxazine-2,4-dione (3i). Yield: 48%
2
2
−1
(
1
1
20.0 mg), yellow solid, mp 196−198 °C; IR (KBr, cm ): 3441, 2923,
764, 1684, 1619, 1515, 1423. H NMR (DMSO-d , 400 MHz) δ
2.08 (s, 1 H), 8.41 (s, 1 H), 8.24 (d, J = 8.4 Hz, 1 H), 7.22 (d, J = 8.4
Hz, 1 H), 2.60 (s, 3 H); C{ H} NMR (DMSO-d , 100 MHz) δ
extracted with EtOAc (3 × 10 mL). The combined organic layers were
1
6
dried over anhydrous Na SO and then evaporated in vacuo. The
2
4
residue was purified by column chromatography on silica gel to afford
the corresponding isatoic anhydride 3 with hexanes/EtOAc (3/1) as
the eluent.
13
1
6
1
95.8, 159.4, 146.9, 144.7, 136.0, 131.9, 129.6, 115.7, 110.4, 26.5.
+
HRMS calcd (ESI) m/z for C H NO : [M − H] 204.0302, found
204.0310. MS m/z (relative intensity) 205 (45), 190 (15), 161 (60),
10
6
4
1
H-Benzo[d][1,3]oxazine-2,4-dione (3a). Yield: 68% (22.2 mg),
1
white solid, mp 205−207 °C; H NMR (DMSO-d , 400 MHz) δ 11.73
6
1
46 (100), 90 (25), 63 (25).
(
7
s, 1 H), 7.90 (d, J = 7.6 Hz, 1 H), 7.73 (t, J = 7.6 Hz, 1 H), 7.24 (t, J =
.2 Hz, 1 H), 7.14 (d, J = 8.0 Hz, 1 H); 1 C{ H} NMR (DMSO-d ,
3
1
6-Nitro-1H-benzo[d][1,3]oxazine-2,4-dione (3j). Yield: 38%
6
1
(
15.8 mg), yellow solid, mp 232−234 °C; H NMR (DMSO-d , 400
6
1
00 MHz) δ 159.9, 147.1, 141.4, 137.0, 128.9, 123.5, 115.3, 110.3.
+
MHz) δ 12.37 (s, 1 H), 8.56 (s, 1 H), 8.52 (d, J = 8.8 Hz, 1 H), 7.30
HRMS calcd (ESI) m/z for C H NNaO : [M + Na] 186.0162, found
8
5
3
13
1
(
d, J = 9.2 Hz, 1 H); C{ H} NMR (DMSO-d , 100 MHz) δ 158.7,
1
6
86.0167. MS m/z (relative intensity) 163 (38), 119 (100), 92 (70),
4 (30).
6
1
46.6, 146.1, 142.4, 131.3, 124.6, 116.7, 111.2. HRMS calcd (ESI) m/z
+
for C H N NaO : [M + Na] 231.0012, found 231.0015. MS m/z
6
-Fluoro-1H-benzo[d][1,3]oxazine-2,4-dione (3b). Yield: 79%
8
4
2
5
1
(relative intensity) 208 (30), 182 (90), 164 (100), 134 (20), 106 (25),
(
28.7 mg), white solid, mp 225−227 °C; H NMR (DMSO-d , 400
MHz) δ 11.79 (s, 1 H), 7.64 (s, 2 H), 7.16 (d, J = 4.0 Hz, 1 H);
C{ H} NMR (DMSO-d , 100 MHz) δ 159.2, 157.6 (d, J = 240.3
6
9
0 (48), 63 (35).
1
3
1
6-Methyl-1H-benzo[d][1,3]oxazine-2,4-dione (3k). Yield: 51%
6
CF
1
(
18.0 mg), white solid, mp 216−218 °C; H NMR (DMSO-d , 400
6
Hz), 146.8, 138.1, 124.8 (d, JCF = 24 Hz), 117.6 (d, JCF = 7.7 Hz),
14.0 (d, JCF = 24.1 Hz), 111.5 (d, J = 8.2 Hz). HRMS calcd (ESI)
MHz) δ 11.64 (s, 1 H), 7.68 (s, 1 H), 7.54 (d, J = 8.4 Hz, 1 H), 7.03
1
CF
13
1
+
(d, J = 8.4 Hz, 1 H), 2.31 (s, 3 H); C{ H} NMR (DMSO-d , 100
m/z for C H FNNaO : [M + Na] 204.0067, found 204.0064. MS m/
6
8
4
3
MHz) δ 159.9, 147.1, 139.2, 137.9, 133.0, 128.3, 115.3, 110.0, 20.1.
z (relative intensity) 181 (35), 137 (100), 109 (60), 82 (48).
-Chloro-1H-benzo[d][1,3]oxazine-2,4-dione (3c). Yield: 80%
+
HRMS calcd (ESI) m/z for C H NNaO : [M + Na] 200.0318, found
6
9
7
3
1
200.0319. MS m/z (relative intensity) 177 (30), 133 (100), 104 (75),
(
31.5 mg), white solid, mp 247−249 °C; H NMR (DMSO-d , 400
6
7
8 (30), 51 (25).
MHz) δ 11.87 (s, 1 H), 7.84 (s, 1 H), 7.76 (d, J = 8.4 Hz, 1 H), 7.15
d, J = 8.8 Hz, 1 H); 1 C{ H} NMR (DMSO-d , 100 MHz) δ 159.0,
3
1
6,8-Dimethyl-1H-benzo[d][1,3]oxazine-2,4-dione (3l). Yield:
(
6
1
4
4% (16.8 mg), white solid, mp 212−214 °C; H NMR (DMSO-d ,
1
46.8, 140.3, 136.7, 127.7, 127.2, 117.5, 112.0. HRMS calcd (ESI) m/z
6
+
400 MHz) δ 10.98 (s, 1 H), 7.57 (s, 1 H), 7.41 (s, 1 H), 2.29 (s, 6 H);
for C H ClNNaO : [M + Na] 219.9772, found 219.9771. MS m/z
8
4
3
13
1
C{ H} NMR (DMSO-d , 100 MHz) δ 160.0, 147.3, 139.0, 137.6,
(
relative intensity) 197 (46), 153 (100), 125 (48), 63 (50).
-Chloro-1H-benzo[d][1,3]oxazine-2,4-dione (3d). Yield: 57%
6
7
132.5, 126.1, 124.3, 110.2, 19.9, 16.9. HRMS calcd (ESI) m/z for
1
+
(
22.4 mg), white solid, mp 238−240 °C; H NMR (DMSO-d , 400
C H NNaO : [M + Na] 214.0475, found 214.0481. MS m/z
10 9 3
6
MHz) δ 11.86 (s, 1 H), 7.90 (d, J = 8.4 Hz, 1 H), 7.28 (d, J = 8.0 Hz, 1
(relative intensity) 191 (50), 147 (60), 119 (100), 104 (35), 91 (35),
66(20).
H), 7.13 (s, 1 H); 13C{ H} NMR (DMSO-d , 100 MHz) δ 159.2,
1
6
1
47.0, 142.6, 141.2, 130.9, 123.7, 114.8, 109.5. HRMS calcd (ESI) m/z
1H-Naphtho[2,1-d][1,3]oxazine-1,3(4H)-dione (3m). Yield:
+
1
for C H ClNNaO : [M + Na] 219.9772, found 219.9775. MS m/z
56% (23.7 mg), brown solid, mp 265−267 °C; H NMR (DMSO-
8
4
3
(
relative intensity) 197 (48), 153 (100), 126 (80), 63 (50).
-Bromo-1H-benzo[d][1,3]oxazine-2,4-dione (3e). Yield: 46%
d , 400 MHz) δ 12.07 (s, 1 H), 9.15 (d, J = 8.8 Hz, 1 H), 8.30 (d, J =
6
6
8.4 Hz, 1 H), 8.00 (d, J = 7.6 Hz, 1 H), 7.76 (t, J = 7.6 Hz, 1 H), 7.58
1
13
1
(
22.2 mg), white solid, mp 230−232 °C; H NMR (DMSO-d , 400
(t, J = 7.2 Hz, 1 H), 7.31 (d, J = 8.8 Hz, 1 H); C{ H} NMR (DMSO-
d6, 100 MHz) δ 159.2, 147.5, 144.2, 138.6, 130.4, 130.1, 129.6, 129.3,
125.7, 123.8, 115.5, 101.6. HRMS calcd (ESI) m/z for C H NNaO :
6
MHz) δ 11.86 (s, 1 H), 7.97 (s, 1 H), 7.88 (d, J = 8.0 Hz, 1 H), 7.09
1
(
d, J = 8.8 Hz, 1 H); 13C{ H} NMR (DMSO-d , 100 MHz) δ 158.8,
6
12
7
3
4
199
dx.doi.org/10.1021/jo500417u | J. Org. Chem. 2014, 79, 4196−4200

The Journal of Organic Chemistry
Note
+
[
(
M + Na] 236.0318, found 236.0321. MS m/z (relative intensity) 213
(7) (a) Brouillette, Y.; Martinez, J.; Lisowski, V. Eur. J. Org. Chem.
2009, 3487. (b) Kappe, T.; Stadlbauer, W. Adv. Heterocycl. Chem.
1981, 28, 127. (c) Coppola, G. M. Synthesis 1980, 505.
70), 169 (100), 141 (50), 114 (60), 88 (20), 71 (30).
-Methoxy-1H-benzo[d][1,3]oxazine-2,4-dione (3n). Yield:
1% (35.0 mg), white solid, mp 206−208 °C; H NMR (DMSO-d ,
00 MHz) δ 11.61 (s, 1 H), 7.38 (d, J = 7.2 Hz, 1 H), 7.33 (s, 1 H),
.10 (d, J = 8.8 Hz, 1 H), 3.80 (s, 3 H); HRMS calcd (ESI) m/z for
C H NNaO : [M + Na] 216.0267, found 216.0271. MS m/z (relative
intensity) 193 (40), 148 (75), 121 (30), 106 (100), 79 (20), 51 (20).
6
1
9
4
7
(8) (a) Guan, Z.-H.; Chen, M.; Ren, Z.-H. J. Am. Chem. Soc. 2012,
134, 17490. (b) Pd-catalyzed oxidative carbonylation of simple
anilines produces N,N′-disubstituted ureas or carbamates; see ref 9b.
(9) (a) Chen, M.; Ren, Z.-H.; Wang, Y.-Y.; Guan, Z.-H. Angew.
Chem., Int. Ed. 2013, 52, 14196. (b) Guan, Z.-H.; Lei, H.; Chen, M.;
Ren, Z.-H.; Bai, Y.; Wang, Y.-Y. Adv. Synth. Catal. 2012, 354, 489.
(c) Valli, V. L. K.; Alper, H. Organometallics 1995, 14, 80. (d) Fukuoka,
S.; Chono, M.; Kohno, M. J. Org. Chem. 1984, 49, 1458.
6
+
9
7
4
ASSOCIATED CONTENT
Supporting Information
Copies of H and C NMR spectra for products. This material
is available free of charge via the Internet at http://pubs.acs.org.
■
*
S
1
13
(10) (a) Collman, J. P.; Hutchison, J. E.; Lopez, M. A.; Tabard, A.;
Guilard, R.; Seok, W. K.; Ibers, J. A.; L’Her, M. J. Am. Chem. Soc. 1992,
1
14, 9869. (b) Reddy, K. S. K.; Narender, N.; Rohitha, C. N.; Kulkarni,
S. J. Synth. Commun. 2008, 38, 3894.
AUTHOR INFORMATION
Corresponding Author
E-mail: guanzhh@nwu.edu.cn.
Notes
■
(11) (a) Lafrance, M.; Lapointe, D.; Fagnou, K. Tetrahedron 2008,
64, 6015. (b) Lafrance, M.; Fagnou, K. J. Am. Chem. Soc. 2006, 128,
16496.
*
(12) (a) Ohashi, S.; Sakaguchi, S.; Ishii, Y. Chem. Commun. 2005,
4
86. (b) Lu, W.; Yamaoka, Y.; Taniguchi, Y.; Kitamura, T.; Takaki, K.;
The authors declare no competing financial interest.
Fujiwara, Y. J. Organomet. Chem. 1999, 580, 290. (c) Taniguchi, Y.;
Yamaoka, Y.; Nakata, K.; Takaki, K.; Fujiwara, Y. Chem. Lett. 1995,
345. (d) Jintoku, T.; Taniguchi, H.; Fujiwara, Y. Chem. Lett. 1987,
1159.
ACKNOWLEDGMENTS
This work was supported by generous grants from the National
Natural Science Foundation of China (NSFC-21272183,
■
2
1002077) and Fund of the Rising Stars of Shanxi Province
(2012KJXX-26).
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