Chemoselective oxidation of 1-alkenylisatins with m-chloroperbenzoic acid. Synthesis of new derivatives of isatoic anhydride

Article abstract of DOI:10.1134/S1070363215090030

Oxidation of alkyl- and alkenylisatins with m-chloroperbenzoic acid proceeds with high chemoselectivity leading to the formation of 1-substituted isatoic anhydrides (benzo[d][1,3]oxazine-2,4-diones) without epoxidation of the double bond of the alkenyl su

Full text of DOI:10.1134/S1070363215090030

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 9, pp. 2030–2036. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.V. Bogdanov, T.I. Sadykov, L.I. Musin, A.R. Khamatgalimov, D.B. Krivolapov, A.B. Dobrynin, V.F. Mironov, 2015, published in
Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 9, pp. 1446–1452.
To the 85th Anniversary of birthday of late Yu.G. Gololobov
Chemoselective Oxidation of 1-Alkenylisatins
with m-Chloroperbenzoic Acid.
Synthesis of New Derivatives of Isatoic Anhydride
A. V. Bogdanov, T. I. Sadykov, L. I. Musin, A. R. Khamatgalimov,
D. B. Krivolapov, A. B. Dobrynin, and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre, Russian Academy of Sciences,
ul. Akademika Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: abogdanov@inbox.ru
Received July 17, 2015
Abstract—Oxidation of alkyl- and alkenylisatins with m-chloroperbenzoic acid proceeds with high chemo-
selectivity leading to the formation of 1-substituted isatoic anhydrides (benzo[d][1,3]oxazine-2,4-diones)
without epoxidation of the double bond of the alkenyl substituent. This result is in accordance with the data of
DFT quantum chemical calculations using the B3LYP functional in conjunction with the basis set of atomic
orbitals 6-31G(d,p). The structure of the synthesized heterocyclic compounds was proved by NMR and X-ray
diffraction data.
Keywords: isatin, ring expansion reaction, benzoxazinediones, X-ray diffraction
DOI: 10.1134/S1070363215090030
Isatoic anhydride (benzo[d][1,3]oxazine-2,4-dione)
and its derivatives are convenient building blocks in
organic synthesis. One of the main areas of their use is
the synthesis of anthranilic acids used as corrosion
inhibitors [1], in the production of pigments and dyes
[2], etc. The high reactivity of 1,3-oxazine-2,4-dione
moiety allows to use these compounds in the synthesis
of various nitrogen-containing heterocyclic structures
like quinazoline, quinazolone, quinazolinedione,
benzodiazepines, quinolinone, and triptanthrin
derivatives [3–6].
action of various peroxides like hydrogen peroxide in
acetic acid [12–14], peracetic [15, 16], monoperoxy-
phthalic [17] or m-chloroperbenzoic [18–20] acids. In
contrast to the above examples, the oxidation of 1-
methyl-4,5,6-tri-methoxyisatin with m-chloroper-
benzoic acid in di-chloromethane afforded not the
corresponding isatoic anhydride, but substituted 1,4-
benzoxazine-2,3(4H)-dione [21]. The most popular
method of the synthesis of the desired heterocycles is
the reaction of anthranilic acid with phosgene or
triphosgene. This approach allowed to obtain a number
of substituted benzoxazinediones, which further were
used the synthesis of heterocyclic and acyclic
compounds exhibiting anti-allergic [22], anti-cancer
[23–25], anticholinesterase [26, 27], antiviral [28, 29],
antidiabetic [30, 31], and insecticidal [32] activity.
Another simple method of the synthesis of isatoic
anhydride involves the use of cyclic derivatives of
phthalic acid like phthalimide and phthalic anhydride.
In the first case, phthalimide is oxidized with sodium
hypochlorite [33]; in the second case, reaction of
phthalic anhydride with trimethylsilylazide occurring
To date there are several approaches to the synthesis of
benzo[d][1,3]oxazine-2,4-dione. The first isatoic
anhydride synthesis was carried out in 1884 via isatin
oxidation with chromium trioxide in acetic acid in the
presence of acetic anhydride [7, 8]. Later, this approach
was used for the synthesis of isatoic anhydride
derivatives with benzo fragment containing halogen
atoms [9, 10] or a trifluoroacetamide group [11].
Isatins with substituted aromatic moiety can be
oxidized to the corresponding isatoic anhydrides by the
2030

CHEMOSELECTIVE OXIDATION OF 1-ALKENYLISATINS
2031
Scheme 1.
C(O)OOH
O
O
5
4
4a
8a
6
7
O
2
O +
CHCl3
N
N
R
O
Cl
−3-ClC6H4COOH
8
R
4−6
1−3
R = CH2CH=CH2 (1, 4), CH2CH=CHPh (2, 5), C14H29 (3, 6).
Scheme 2.
H
+O
C
O
O
HO
HO
H
C
4
O
O
R2
R2
3a
7a
O
O
O
H+
5
6
O
3
O
O +
O
2
O C
N
N
N
7
R2
R1
R1
R1
1−3
A
B
O
HO
O−
O
O
− R2COOH
− H+
N
N
O
R1
R1
4−6
C
through the intermediate formation of 2-carboxy-
phenylisocyanate is used [34–39]. The disadvantage of
this approach is the formation of two regioisomeric
isatoic anhydrides, when unsymmetrically substituted
phthalic anhydrides were used as precursors.
Scheme 2 shows a plausible mechanism of the
formation of compounds 4–6. In the first stage the
reaction proceeds probably according to the Bayer–
Villiger reaction type and involves the formation of
adduct A due to the addition of the peroxy acid to the
carbonyl group of isatin. Further intermediate A
undergoes protonation with m-chloroperbenzoic acid
or 3-chloroperbenzoic acid followed by the elimination
of carboxylic acid from its molecule to form
intermediate B. Then intermediate B undergoes intra-
molecular nucleophilic attack of alkoxide anion at the
carbonyl group followed by deprotonation and ring
extension to give the final compound 4–6.
In recent years, some approaches to the synthesis of
this class of heterocycles were developed on the basis
of palladium-catalyzed carbonylation of o-iodoaniline,
anthranilic acids, or N-alkylanilines with carbon
monoxide [40–42] or the oxidation of indole
derivatives with oxone [43].
In this work we investigated the reaction of 1-
alkenyl- and 1-alkyl-substituted isatins with m-
chloroperbenzoic acid. Thus, reaction of isatins 1 and
2, bearing alkenyl groups capable of epoxidation, with
m-chloroperbenzoic acid led to the formation of the
corresponding isatoic anhydride derivatives 4 and 5 as
sole reaction products (Scheme 1). It should be noted
that the formation of the corresponding products of the
double bond epoxidation as described in [44, 45] was
not observed.
The oxidation of the 1,2-dicarbonyl moiety instead
of the alkenyl group may be due to the higher electro-
philicity of the carbonyl group in position 3 of the
heterocycle. Thus, quantum-chemical calculations of
atomic charges in compounds 1 and 2 based on the
density functional theory (DFT) with B3LYP func-
tional in conjunction with the basis set of atomic
orbitals 6-31G(d,p) showed that the largest positive
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015

2032
BOGDANOV et al.
The structures of compounds 4–6 were proved by
1H and 13C NMR spectroscopy methods. Thus, in the
13C–{1H} NMR spectra the signals at 158 ppm
corresponded to the carbonyl group in the position 4 of
the heterocycle. In the spectra of initial isatins the
signal of this carbon atom appeared in a weak field (δC =
180–185 ppm) characteristic of the ketone carbonyl
1
group. Comparing the H NMR spectra of the starting
compounds and isatins 4–6 the shift of the signal of H5
proton from 7.63 to 8.16–8.18 ppm may be due to the
occurrence of intramolecular hydrogen bond between
the proton and the neighboring carbonyl group.
The spatial geometry of compounds 4 and 6 was
established by X-ray diffraction analysis (Figs. 1 and
2). Suitable crystals were obtained by recrystallization
from hexane–chloroform mixture. Six-membered
heterocycles in compounds 4 and 6 are planar within
0.04(1) and 0.05(2) Å, respectively. The oxygen atoms
of the carbonyl groups are in the plane of heterocycles.
The substituents at the nitrogen atom in the crystals of
compounds 4 and 6 are located orthogonally to the
heterocycle plane: torsion angles C2N1C9C10 are 94.7(9)°
and 92(1)°, respectively.
Fig. 1. Molecular geometry of compound 4 in a crystal.
The selected bond lengths, bond and torsion angles: O2–C2
1.18(1), C8–C8A 1.40(1), O3–C2 1.36(1), C9–C10 1.55(1),
O3–C4 1.42(1), C10–C11 1.22(1), O4–C4 1.20(1), N1–C2
1.37(1), N1–C8A 1.403(9), N1–C9 1.450(9), C4–C4A 1.40(1),
C4A–C8A 1.401(9) Å; C2N1C8A 122.6(6)°, C2N1C9 114.6(6)°,
C8AN1C9 122.8(5)°, O2C2O3 115(1)°, O2C2N1 127(1)°,
O3C2N1 117.5(9)°, O3C4O4 110.2(9)°, O3C4C4A 119.3(7)°,
O4C4C4A 130.5(9)°, C9N1C2O2 8(2)°, N1C9C10C11 134(1)°.
charge is localized on the atoms C3, C2 and C7a (see
table, positive charges shown in italics). Full geometry
optimization of the studied molecular structures was
carried out without restrictions on the symmetry by the
program GAUSSIAN'03 [46]. Calculation and analysis
of normal vibrations confirmed the compliance of the
optimized structure to the energy minimum on the
potential energy surface.
In summary, the oxidation of 1-alkyl- and 1-alkenyl
isatins with m-chloroperbenzoic acid proceeded
chemoselectively at the carbonyl group to form 1-sub-
stituted isatoic anhydrides as the sole reaction product.
EXPERIMENTAL
IR spectra were recorded on a Bruker Vector-22
spectrometer from the sample suspended in mineral oil
or from KBr pellets. 1H and 13C NMR spectra (CDCl3)
were registered on a Bruker Avance-400 instrument
(400 and 100.6 MHz, respectively). Melting points
were measured on a SMP10 Stuart instrument.
Elemental analysis was performed using a CHNS-3
analyzer.
The calculated Mulliken atomic charges in compounds 1
and 2
Compound
Atomа
1
2
N
–0.590708
+0.558318
+0.324226
+0.032433
–0.108488
–0.096359
–0.085514
–0.107445
+0.318995
–0.469785
–0.431531
–0.589774
+0.557511
+0.324236
+0.031750
–0.108703
–0.096400
–0.085628
–0.106277
+0.319937
–0.470499
–0.432127
C2
С3
С3a
С4
С5
С6
С7
С7а
O1
O2
Alkylisatins 1 and 3 were prepared according to
procedures described in [47, 48].
1-Cinnamylindoline-2,3-dione (2). To a solution
of 2.94 g (0.02 mol) of isatin in 20 mL of DMF with
stirring at 10°C was slowly added 0.84 g (0.02 mol) of
sodium hydride (60% suspension in mineral oil). After
30 min, 2.92 mL (0.02 mol) of cinnamyl chloride was
added to the resulting purple solution followed by
stirring at room temperature for 3 h. The reaction
mixture was poured into 100 g of crushed ice. Next,
the resulting precipitate was filtered off, washed with
a The numbering of the atoms is given according to the Scheme 2.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015

CHEMOSELECTIVE OXIDATION OF 1-ALKENYLISATINS
2033
C6
C7
C8
C5
C22
C20
C21
C18
C19
C16
C17
C8а
N1
C4а
C4
C14
C15
C10
C11
C12
C13
O4
C9
C2
O3
O2
Fig. 2. Molecular geometry of compound 6 in a crystal. The selected bond lengths, bond and torsion angles: O2–C2 1.21(2), O3–C2
1.34(2), O3–C4 1.34(2), O4–C4 1.18(2), N1–C2 1.45(2), N1–C8A 1.39(2), N1–C9 1.48(2), C4–C4A 1.48(2), C4A–C8A 1.35(2) Å; C2–N1–C8A
117(1)°, C2N1C9 119(1)°, C8AN1C9 124(1)°, O2C2O3 124(1)°, O2C2N1 118(1)°, O3C2N1 119(1)°, O3C4O4 117(1)°, O3C4C4A 116(1)°,
O4C4C4A 127(1)°, C9N1C2O2 9(2)°, N1C9C10C11 169(1)°.
hexane, and dried in a vacuum (18 mmHg). Yield 4.94 g
(94%), orange powder, mp 133–135°C. IR spectrum
(KBr), ν, cm–1: 3091, 3037, 2918, 2853, 1725, 1607,
for 2 h. After cooling, a saturated aqueous potassium
carbonate solution (10 mL) was added to the reaction
mixture. The organic layer was separated and
evaporated. The residue was recrystallized from
chloroform–hexane mixture (9 : 1).
1
1469, 1370, 1347, 1172, 1094. H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 4.54 d.d (2H, NCH2, 3JHH 6.0,
3
3
4JHH 1.5), 6.20 d.t (1H, C=CH, JHH 6.0, JHH 15.9),
1-Allyl-1H-benzo[d][1,3]oxazine-2,4-dione
(4).
6.70 br.d (1H, C=CH, JHH 15.9), 6.99 d (1H, H7, JHH
3
3
Yield 81%, colorless crystalline powder, mp 103°C. IR
spectrum (paraffin oil), ν, cm–1: 1770, 1722, 1683,
1603, 1493, 1379, 1319, 1247, 1028. 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 4.71 d.t (2H, NCH2,
7.9), 7.13 m (1H, H5, JHH 7.5, JHH 7.6, JHH 0.7),
3
3
4
7.25–7.38 m (5H, Ph), 7.58 d.d.d (1H, H6, JHH 7.8,
3
3JHH 7.9, JHH 1.3), 7.63 d.d (1H, H4, JHH 7.5, JHH
0.8). 13C NMR spectrum (CDCl3), δC, ppm (J, Hz) (the
data given in parentheses are for the 13C–{1H}
spectra): 42.10 t.d.d (s) (NCH2, 1JHC 139.9, 1JHC 140.3,
3JHC 7.6, 2JHC 4.0, 2JHC 4.4), 110.81 d.d.d.d (s) (C7, 1JHC
4
3
4
4
3JHH 5.1, JHH 1.7), 5.27–5.35 m (2H, =CH2), 5.87–
3
5.97 м (1H, =CH), 7.16 br.d (1H, H8, JHH 8.4), 7.30
3
3
4
d.d.d (1H, H6, JHH 7.8, JHH 7.4, JHH 0.9), 7.73 d.d.d
(1H, H7, JHH 7.4, JHH 7.4, JHH 1.6), 8.16 d.d.d (1H,
3
3
4
3
4
4
164.5, JHC 8.0, JHC 1.6, JHC 1.2), 117.61 d.d.t (s)
H5, JHH 7.9, JHH 1.6, JHH 0.4). 13C NMR spectrum
3
4
5
(Cipso, JHC 6.7, JHC 5.6, JHC 1.2), 121.45 d.d.t (s)
3
3
2
(CDCl3), δC, ppm (J, Hz): 158.33 d (s) (C4, JHC 4.0),
3
1
2
2
(CH=CH2, JHC 156.2, JHC 5.6, JHC 1.6), 123.74 d.m
147.72 d.d (s) (C2, JHC 3.7, JHC 4.0), 141.35 m (s)
3
3
(s) (C4, JHC 164.5), 125.32 d.d.d.d (s) (C5, JHC 165.3,
1
1
(C8а), 137.10 d.d.d (s) (C7, JHC 162.1, JHC 8.8, JHC
1
3
2
3JHC 8.6, JHC 1.6, JHC 1.2), 126.44 d.m (Co, JHC
2
2
1
1.5), 130.84 d.d (s) (C5, JHC 167.3, JHC 8.4), 130.07
1
3
158.2, JHC 6.4), 128.16 d.d.t (s) (Cp, JHC 160.9, JHC
3
1
3
d.m (s) (=CH, JHC 158.5), 124.05 d.d (s) (C6, JHC
1
1
7.2, JHC 1.2), 128.61 d.d.d (s) (Cm, JHC 160.5, JHC
2
1
3
3
1
166.2, JHC 7.7), 118.66 t.d.d (s) (=CH2, JHC 154.8,
8.0, 2JHC 1.2), 134.0 d.m (s) (=CH–Ph, 1JHC 151.8, 3JHC
3JHC 5.5, JHC 5.1), 114.44 d.d (s) (C8, JHC 163.6, JHC
3
1
3
5.2, JHC 4.8), 135.72 m (s) (C3a, JHC 6.0), 138.31
3
3
7.3), 111.76 d.d (s) (C4a, JHC 7.7, JHC 7.4), 47.11 t.m
3
3
d.d.d (s) (C6, JHC 161.3, JHC3 7.9, JHC 2.0), 150.76 m
(s) (C7a), 157.88 t (C2=O, JHC 3.2), 183.20 d.t (s)
(C3=O, 3JHC 3.2, 4JHC 1.2). Found, %: C 77.32; H 4.69;
N 5.27. C17H13NO2. Calculated, %: C 77.55; H 4.98; N
5.32.
1
3
2
1
(s) (NCH2, JHC 141.2). Found, %: C 64.87; H 4.28; N
6.69. C11H9NO3. Calculated, %: C 65.02; H 4.46; N
6.89.
1-Cinnamyl-1H-benzo[d][1,3]oxazine-2,4-dione (5).
Yield 89%, beige powder, mp 193–195°C (decomp.).
IR spectrum (KBr), ν, cm–1: 3085, 3042, 1715, 1655,
General procedure for the preparation of
compounds 4–6. To a solution of 2.9 mmol of
substituted isatin in 20 mL of chloroform while stirring
at 0°C was slowly added 0.6 g (3.5 mmol) of m-
chloroperoxybenzoic acid followed by stirring at 60°C
1
1630, 1452, 1378, 1132, 1061. H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 4.87 d.d (2H, NCH2, 3JHH 5.9,
3
3
4JHH 1.5), 6.25 d.t (1H, C=CH, JHH 6.0, JHH 16.0),
3
6.68 br.d (1H, C=CH, JHH 16.0), 7.25–7.37 m (6H,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015

2034
BOGDANOV et al.
3
Ph, H8), 7.41 t (1H, H6, JHH 7.9), 7.74 d.d.d (1H, H7,
3JHH 7.4, 3JHH 7.4, 4JHH 1.6), 8.18 d.d (1H, H5, 3JHH 7.9,
4JHH 1.5). Found, %: C 72.80; H 4.47; N 4.83.
C17H13NO3: Calculated, %: C 73.11; H 4.69; N 5.02.
at the Cambridge Crystallographic Data Center (CCDC
1 415 507).
The crystals of compound 6 were monoclinic,
C22H33NO3, М = 359.49; parameters of the unit cell:
a = 26.83(8), b = 4.903(15), c = 15.79(5) Å; β = 93.52(4)°;
V = 2073(11) Å3, Z = 4; space group P21/c,
F(000) = 784, 2θmax = 54°, R = 0.1656, wR(F2) =
0.3764 (for 4517 independent reflections). The
crystallographic data were deposited at the Cambridge
Crystallographic Data Center (CCDC 1,415,508).
1-Tetradecyl-1H-benzo[d][1,3]oxazine-2,4-dione
(6). Yield 78%, beige powder, mp 90°C. IR spectrum
(KBr), ν, cm–1: 2916, 2849, 1783, 1722, 1603, 1478,
1372, 1324, 1250, 1031. H NMR spectrum (CDCl3),
δ, ppm (J, Hz): 0.88 t (3H, CH3, JHH 7.2), 1.26–1.47
1
3
m (22H, 11CH2), 1.72–1.79 m (2H, CH2), 4.05 t (2H,
NCH2, JHH 7.8), 7.16 d (1H, H8, JHH 8.5), 7.29 m
3
3
(1H, H6, JHH 7.4), 7.75 d.d.d (1H, H7, JHH 7.4, JHH
7.4, 3JHH 1.6), 8.16 d.d (1H, H5, 3JHH 7.9, 4JHH 1.6). 13C
NMR spectrum (CDCl3), δC, ppm (J, Hz): 158.52 d.d
3
3
3
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Science Foundation (grant no. 14-50-00014).
(s) (C4, JHC 4.4, JHC 1.1), 147.70 t (с) (C2, JHC 4.0),
3
4
3
141.40 m (s) (C8а), 137.13 d.d.d (s) (C7, JHC 161.8,
1
3JHC 8.8, JHC 1.8), 130.98 d.d.d.d (s) (C5, JHC 166.5,
2
1
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4
1
166.2, JHC 7.7), 113.83 d.d.t (s) (C8, JHC 162.9, JHC
3
1
3
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