A new polycyclic system containing the 1,4-benzodiazepine and isoindolinone fragments: Synthesis and structure

Article abstract of DOI:10.1007/s11172-011-0258-9

Dehydration of 2-(3,3-dimethyl-1-oxo-2,3,4,5,10,11-hexahydro-1 H-dibenzo[b,e][1,4]-diazepin-11-yl)benzoic acid (3a) and 2-(3,3-dimethyl-1-oxo- 2,3,4,5,10,11-hexahydro-1 H-dibenzo[b,e][1,4]diazepin-11-yl)-5,6- dimethoxybenzoic acid (3b) in boiling acetic or propionic anhydride gave 7,7-dimethyl-4b,7,8,9-tetrahydro-6H-dibenzo[2,3:5,6][1,4]diazepino[7,1-a] -isoindole-5,15-dione (5a) and 1,2-dimethoxy-7,7-dimethyl-4b,7,8,9-tetrahydro- 6H-dibenzo-[2,3:5,6][1,4]diazepino[7,1-a]isoindole-5,15-dione (5b), respectively. The products obtained are representatives of a novel fused pentacyclic system. The structures of compounds 3b and 5a were unambiguously proved by X-ray diffraction.

Full text of DOI:10.1007/s11172-011-0258-9

Russian Chemical Bulletin, International Edition, Vol. 60, No. 8, pp. 1729—1733, August, 2011
1729
A new polycyclic system containing the 1,4ꢀbenzodiazepine
and isoindolinone fragments: synthesis and structure
L. Yu. Ukhin,a K. Yu. Suponitskii,b E. N. Shepelenko,c L. V. Belousova,a Zh. I. Orlova,a and G. S. Borodkina
aResearch Institute of Physical and Organic Chemistry, Southern Federal University,
194/2 prosp. Stachki, 344090 RostovꢀonꢀDon, Russian Federation.
Fax: +7 (863) 243 4776. Eꢀmail: may@ipoc.rsu.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: kirshik@yahoo.com
cSouthern Scientific Center of the Russian Academy of Sciences,
41 ul. Chekhova, 344006 RostovꢀonꢀDon, Russian Federation.
Fax: +7 (863) 243 4776. Eꢀmail: dubon@ipoc.sfedu.ru
Dehydration of 2ꢀ(3,3ꢀdimethylꢀ1ꢀoxoꢀ2,3,4,5,10,11ꢀhexahydroꢀ1Hꢀdibenzo[b,e][1,4]ꢀ
diazepinꢀ11ꢀyl)benzoic acid (3a) and 2ꢀ(3,3ꢀdimethylꢀ1ꢀoxoꢀ2,3,4,5,10,11ꢀhexahydroꢀ1Hꢀ
dibenzo[b,e][1,4]diazepinꢀ11ꢀyl)ꢀ5,6ꢀdimethoxybenzoic acid (3b) in boiling acetic or propionic
anhydride gave 7,7ꢀdimethylꢀ4b,7,8,9ꢀtetrahydroꢀ6Hꢀdibenzo[2,3:5,6][1,4]diazepino[7,1ꢀa]ꢀ
isoindoleꢀ5,15ꢀdione (5a) and 1,2ꢀdimethoxyꢀ7,7ꢀdimethylꢀ4b,7,8,9ꢀtetrahydroꢀ6Hꢀdibenzoꢀ
[2,3:5,6][1,4]diazepino[7,1ꢀa]isoindoleꢀ5,15ꢀdione (5b), respectively. The products obtained
are representatives of a novel fused pentacyclic system. The structures of compounds 3b and 5a
were unambiguously proved by Xꢀray diffraction.
Key words: 3ꢀ(2ꢀaminophenylamino)ꢀ5,5ꢀdimethylcyclohexꢀ2ꢀenꢀ1ꢀone, 2ꢀformylbenzoic
acid, 2ꢀformylꢀ5,6ꢀdimethoxybenzoic (opianic) acid, hexahydrodibenzo[b,e][1,4]diazepines,
hexahydrodibenzo[b,e]isoindolino[3,2ꢀg][1,4]diazepines, Xꢀray diffraction analysis.
Recently,1—3 we have reported on the synthesis of
phthalimidines from arylaminophthalides and Nꢀacylꢀ2ꢀ
formylbenzohydrazones. The present work is devoted to
the use of 2ꢀformylbenzoic acid and 2ꢀformylꢀ5,6ꢀdiꢀ
methoxybenzoic (opianic) acid for the synthesis of a novel
fused system containing the benzodiazepine and phthalꢀ
imidine fragments. It is known that 3ꢀ(2ꢀaminophenylꢀ
amino)ꢀ5,5ꢀdimethylcyclohexꢀ2ꢀenꢀ1ꢀone (1) smoothly
enters into acidꢀcatalyzed condensation with aldehydes at
room temperature to give tricyclic dibenzo[1,4]diazeꢀ
pines in high yields,4 which exhibit narcotic and analgesic
activities.5,6
Using 2ꢀformylbenzoic (2a) and opianic acids (2b) as
the aldehyde component in this reaction, we obtained
2ꢀ(3,3ꢀdimethylꢀ1ꢀoxoꢀ2,3,4,5,10,11ꢀhexahydroꢀ1Hꢀdiꢀ
benzo[b,e][1,4]diazepinꢀ11ꢀyl)benzoic acid (3a) and
2ꢀ(3,3ꢀdimethylꢀ1ꢀoxoꢀ2,3,4,5,10,11ꢀhexahydroꢀ1Hꢀdiꢀ
benzo[b,e][1,4]diazepinꢀ11ꢀyl)ꢀ5,6ꢀdimethoxybenzoic
acid (3b), respectively (Scheme 1). The presence of the
carboxyl function in the starting compounds allowed this
synthesis to be performed without adding acid catalysts.
In boiling acetic or propionic anhydride, these compounds
were easily transformed into 7,7ꢀdimethylꢀ4b,7,8,9ꢀtetraꢀ
hydroꢀ6Hꢀdibenzo[2,3:5,6][1,4]diazepino[7,1ꢀa]isoindoleꢀ
5,15ꢀdione (5a) and 1,2ꢀdimethoxyꢀ7,7ꢀdimethylꢀ4b,
7,8,9ꢀtetrahydroꢀ6Hꢀdibenzo[2,3:5,6][1,4]diazepino[7,1ꢀa]ꢀ
isoindoleꢀ5,15ꢀdione (5b), respectively (see Scheme 1).
These are derivatives of a novel fused pentacyclic system.
Earlier,4 the easy formation of N(10)ꢀacetyl derivatives
has been noted for reactions of analogs of compounds 3a,b
with Ac2O. Apparently, the cyclization 3 → 5 also proꢀ
ceeds through acyl intermediates 4a,b.
Compound 3a obtained according to a known proceꢀ
dure4 has been characterized in a study7 dealing with MS
fragmentation of similar dibenzodiazepinones. Its mass
spectrum contains a peak corresponding to compound 5a.
Structure 5a has been described in a patent,8 though withꢀ
out any mention of its synthesis or properties. Data on
compounds 3b and 5b are lacking in the literature. Strucꢀ
tures 3b and 5a were unambiguously proved by Xꢀray difꢀ
fraction from crystals grown by slow evaporation of their
solutions in acetonitrile.
The general view of structure 5a is shown in Fig. 1. The
central sevenꢀmembered ring has a distorted boat conforꢀ
mation. The C(8), N(1), N(2), and C(10) atoms are coꢀ
planar. The C(15) and C(20) atoms deviate from their
plane by 0.886(4) and 0.822(4) Å, respectively, while the
C(9) atom deviates by 0.113(4) Å; the N(1), C(15), C(20),
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1703—1707, August, 2011.
1066ꢀ5285/11/6008ꢀ1729 © 2011 Springer Science+Business Media, Inc.

1730
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
Ukhin et al.
Scheme 1
R = H (a), OMe (b)
and N(2) atoms are also coplanar. The dimethylcycloꢀ
hexenone fragment at the C(9) and C(10) atoms has a disꢀ
torted halfꢀchair conformation, while the other rings are
planar. The group N(2)—H(2) is involved in the hydrogen
bond N(2)—H(2)...O(1) (H...O, 2.21 Å; N...O, 3.022(2) Å;
the angle N—H...O, 149°), thus forming chains along the
crystallographic direction [101].
The molecules are linked by the hydrogen bond
N(2)—H(2)...N(1S) (H...O, 2.15 Å; N...O, 3.010(5) Å;
the angle N—H...O, 160°).
The central fragment in structure 3b somewhat differs
from that in structure 5a. The sevenꢀmembered ring has
The general view of structure 3b with a solvate acetoꢀ
nitrile molecule in a ratio of 1 : 1 is shown in Fig. 2.
C(1S)
C(2S)
N(1S)
C(19)
C(18)
C(17)
C(18)
H(2)
C(11)
C(19)
H(2)
C(17)
C(20)
N(2)
C(9)
C(11)
C(12)
C(15)
C(20)
C(10)
C(16)
C(16)
H(1)
C(12)
C(21)
N(2)
C(21)
C(10)
C(15)
N(1)
C(8)
N(1)
C(9)
C(7)
C(22)
O(1)
C(13)
C(14)
C(13)
C(14)
C(8)
O(1)
C(22)
C(2)
O(2)
C(1)
O(3)
C(1)
C(6)
C(5)
C(24)
O(2)
C(7)
C(4)
C(3)
C(2)
C(3)
C(6)
H(3)
O(4)
C(5)
O(5)
C(4)
C(23)
Fig. 1. General view of structure 5a with atomic thermal disꢀ
placement ellipsoids (p = 50%).
Fig. 2. General view of structure 3b with atomic thermal disꢀ
placement ellipsoids (p = 50%).

Synthesis of isoindolino[3,2ꢀg][1,4]diazepines
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
1731
a skew boat conformation. The N(1), C(15), C(20), and
N(2) atoms are coplanar (as in 5a), while the C(8), N(1),
N(2), and C(10) atoms are not. The dimethylcycloꢀ
hexenone fragment has nearly the same conformation as
in 5a; all the aromatic rings are planar. The carboxy group
is far off the plane of the adjacent benzene ring: the torsion
angle C(3)—C(2)—C(1)—O(1) is 116.6(4)°. Apparently,
the orientation of the carboxy group is due to a coopꢀ
erative effect of its steric interaction with the nearest
methoxy group, the intramolecular hydrogen bond
N(1)—H(1)...O(1) (H...O, 2.16 Å; N...O, 2.928(4) Å; the
angle N—H...O, 144°), and the strong intermolecular
hydrogen bond O(3)—H(3)...O(2) (–x, 1 – y, z – 0.5) (H...O,
1.70 Å; O...O, 2.534(3) Å; the angle O—H...O, 168°),
which gives rise to chains along the axis c.
protons at the C(11) and N(10) atoms (see Ref. 4), while
the corresponding signals in the spectra of compounds
3a,b are two singlets.
The signals in the 1H NMR spectrum of compound 3a
1
were assigned from 2D H—1H COSY experiment. To
assign the signals in the 13C NMR spectra, we used 2D
1H—13C correlation experiments (HSQC and HMBC).
Chemical shifts in the 15N NMR spectrum were deterꢀ
1
mined using H—15N HMBC experiment. The data obꢀ
tained are summarized in Table 1.
The 1H—15N HMBC spectrum shows a cross peak for
the N(5) atom as a doublet with JN(5),H(5) = 90 Hz. The
absence of cross peaks for the N(10) atom in the 2D
1H—15N HMBC spectrum is probably due to an exchange
between the protons of the groups O(8´)H (δ 13.25) and
N(10)H (δ 5.56) and the protons of water (δ 3.37) present
in the solvent (DMSOꢀd6). Because of this, the signals of
The 1H NMR spectra of compounds 3a,b in DMSOꢀd6
1
are generally similar to the H NMR spectrum of their
1
analog containing unsubstituted phenyl at the C(11)
atom.4 As in this analog, one CH2 group in compounds
3a,b is manifested as a singlet, while the other, as two
doublets with J = 16 Hz (the AB system). However, their
1H NMR spectra show specific features because of the
presence of the carboxy group in the orthoꢀposition of the
these protons are broadened in the H NMR spectrum.
The exchange process was detected using an EXSY experꢀ
iment (exchange spectroscopy). The EXSY spectrum conꢀ
tain cross peaks for three groups of the protons involved in
the exchange: O(8´)H, N(10)H, and H2O (Fig. 3).
To find out whether compound 3a behaves like this beꢀ
cause of the orthoꢀposition of the carboxy group in the phenyl
substituent, we synthesized its paraꢀanalog 3c (Scheme 2).
1
phenyl substituent. The H NMR spectrum of the above
phenyl analog shows, as expected, two doublets for the
δ
3
4
5
6
7
8
9
10
11
12
13
14
14 13 12 11 10
9
8
7
6
5
4
3
δ
Fig. 3. 2D EXSY spectrum of the intermolecular exchange between the protons of the groups O(8´)H (δ 13.25), N(10)H (δ 5.56), and
H2O (δ 3.37) for compound 3a.

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
Ukhin et al.
Table 1. 1H, 13C, and 15N NMR spectra of compound 3a in
DMSOꢀd6
spectrum of compound 3c were recorded on an AVANCEꢀ600
spectrometer (Bruker). Mass spectra were measured on a Finniꢀ
gan MAT INCOS 50 instrument (direct inlet probe).
No. of
NMR, δ
2ꢀ(3,3ꢀDimethylꢀ1ꢀoxoꢀ2,3,4,5,10,11ꢀhexahydroꢀ1Hꢀdiꢀ
benzo[b,e][1,4]diazepinꢀ11ꢀyl)benzoic acid (3a). A hot solution
of 2ꢀformylbenzoic acid 2a (0.75 g, 5 mmol) in MeOH (5 mL)
was added to a hot solution of compound 1 (1.15 g, 5 mmol) in
MeOH (5 mL). The mixture was heated to boiling and cooled
with ice water, while triturating with a rod. The precipitate that
formed was filtered off, washed with cold MeOH, and dried.
The yield of compound 3a was 1.4 g (73%), colorless solid, m.p.
186—188 °C (from MeNO2) (cf. Ref. 7: m.p. 179—181 °C).
Found (%): C, 72.83; H, 6.21; N, 7.82. C22H22N2O3. Calculatꢀ
ed (%): C, 72.91; H, 6.21; N, 7.73. IR, ν/cm–1: 3884, 3336, 3289
(NH), 1680, 1667, 1624 (CO), 1602, 1573, 1519 (arom.).
1H NMR (DMSOꢀd6), δ: 1.01, 1.08 (both s, 6 H, Me); 2.03, 2.16
(both d, 2 H, CH2, J = 16.0 Hz); 2.62 (s, 2 H, CH2); 5.56 (s, 1 H,
N(10)H); 6.20 (s, 1 H, C(11)H); 6.25 (d, 1 H, CH arom.,
J = 7.6 Hz); 6.50—7.50 (m, 6 H, CH arom.); 7.79 (d, 1 H,
CH arom., J = 7.0 Hz); 8.96 (s, 1 H, N(5)H); 13.50 (br.s, 1 H,
OH). MS, m/z: 362 [M]+.
2ꢀ(3,3ꢀDimethylꢀ1ꢀoxoꢀ2,3,4,5,10,11ꢀhexahydroꢀ1Hꢀdiꢀ
benzo[b,e][1,4]diazepinꢀ11ꢀyl)ꢀ5,6ꢀdimethoxybenzoic acid (3b)
(solvate with MeCN) was obtained from opianic acid 2b (0.46 g,
2.5 mmol) in MeCN (3 mL) and compound 1 (0.6 g, 2.6 mmol)
in MeCN (3 mL) as described for the synthesis of compound 3a.
Crystallization was promoted by using seed crystals. The yield of
compound 3b was 0.83 g (72%), light yellow solid, m.p. 150—155 °C
(foaming). Found (%): C, 67.63; H, 6.25; N, 8.72. C24H26N2O5•
•MeCN (C26H29N3O5). Calculated (%): C, 67.37; H, 6.31;
N, 9.06. IR, ν/cm–1: 3340, 3312, 3247 (NH), 2253 (CN), 1682,
1630 (CO), 1610, 1572, 1485 (arom.). 1H NMR (DMSOꢀd6), δ:
1.05, 1.13 (both s, 6 H, Me); 1.98 (s, 3 H, MeCN); 2.02, 2.13
(both d, 2 H, CH2, J = 16.0 Hz); 2.59 (s, 2 H, CH2); 3.69, 3.77
(both s, 6 H, OMe); 4.87 (s, 1 H, N(10)H); 5.58 (s, 1 H, C(11)H);
6.35 (m, 2 H, CH arom.); 6.57 (m, 3 H, CH arom.); 6.96 (m, 1 H,
CH arom.); 8.75 (s, 1 H, N(5)H). MS, m/z: 422 [M]+.
the atom
1H
—1
2.09
—1
2.64
—1
8.96
—1
7.04
6.64
6.56
6.25
—1
5.56
6.20
—1
13C
15N
1
2
3
4
4a
5
5a
6
7
8
192.31
149.53
131.84
144.22
155.13
—
131.39
120.11
120.37
123.03
120.63
137.47
—
154.96
109.36
145.09
126.36
131.07
126.38
130.46
130.03
169.68
—
—
—
—
—
—
122.0
—
—
—
—
—
—
182.10
—
—
—
—
—
—
9
9a
10
11
11a
1´
2´
3´
4´
5´
6´
7´
8´
12
13
—1
6.77
7.15
7.13
7.79
—1
—
—
—
—
—
—
—1
13.25
1.08
1.01
128.23
127.44
Scheme 2
4ꢀ(3,3ꢀDimethylꢀ1ꢀoxoꢀ2,3,4,5,10,11ꢀhexahydroꢀ1Hꢀdiꢀ
benzo[b,e][1,4]diazepinꢀ11ꢀyl)benzoic acid (3c) (solvate with
MeOH). A hot solution of compound 1 (1.15 g, 5 mmol) in
MeOH (5 mL) was added to a hot solution of 4ꢀformylbenzoic
acid (0.75 g, 5 mmol) in MeOH (20 mL). After the reaction
mixture was brought to boiling, the formation of a colorless crysꢀ
talline precipitate was observed. The reaction mixture was reꢀ
fluxed for 1 min and cooled to room temperature. The preꢀ
cipitate was filtered off, washed with MeOH and light petroꢀ
leum, and dried. The yield of compound 3c was 1.35 g (75%),
m.p. 262—264 °C. Found (%): C, 70.05; H, 6.71; N, 7.25.
C22H22N2O3•MeOH (C23H26N2O4). Calculated (%): C, 70.03;
H, 6.64; N, 7.10. IR, ν/cm–1: 3409, 3281, 3238 (OH, NH), 1679
(CO), 1605, 1588, 1503 (arom.). 1H NMR (DMSOꢀd6), δ: 1.02,
1.07 (both s, 6 H, Me); 2.08, 2.18 (both d, 2 H, CH2, J = 16.0 Hz);
2.59 (s, 2 H, CH2); 3.15 (d, 3 H, Me (MeOH), J = 5.2 Hz); 4.11
(q, 1 H, OH (MeOH), J = 5.2 Hz); 5.72 (d, 1 H, N(10)H,
J = 5.5 Hz); 6.25 (d, 1 H, C(11)H, J = 5.5 Hz); 6.50 (dd, 1 H,
CH arom., 3J = 7.4 Hz, 4J = 2.0 Hz); 6.57 (m, 2 H, CH arom.);
6.92 (dd, 1 H, CH arom., 3J = 7.6 Hz, 4J = 1.8 Hz); 7.16 (d, 2 H,
C(2´)H, C(6´)H, J = 8.5 Hz); 7.66 (d, 2 H, C(3´)H, C(5´)H,
J = 8.5 Hz); 8.83 (s, 1 H, N(5)H); 12.71 (s, 1 H, COOH).
7,7ꢀDimethylꢀ4b,7,8,9ꢀtetrahydroꢀ6Hꢀdibenzo[2,3:5,6][1,4]ꢀ
diazepino[7,1ꢀa]isoindoleꢀ5,15ꢀdione (5a). A. A mixture of comꢀ
1
As expected, the H NMR spectrum of compound 3c
has a common shape with two doublets for the H(10) and
H(11) protons. This suggests that the anomalous features
in the H and 15N NMR spectra of compound 3a result
from prototropic rotation of the carboxy group about the
σꢀbond to the phenyl substituent, which brings about rapid
exchange of the proton at the N(10) atom.
1
Experimental
IR spectra were recorded on a Varian Excalibur 3100 FTꢀIR
instrument (ATRꢀFTIR). The H NMR spectra of compounds
3b and 5a,b were recorded on a UNITYꢀ300 spectrometer (Varian).
The 1H and 13C NMR spectra of compound 3a and the 1H NMR
1

Synthesis of isoindolino[3,2ꢀg][1,4]diazepines
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
1733
Table 2. Crystallographic parameters and the data collection
statistics for compounds 3b and 5a
1,2ꢀDimethoxyꢀ7,7ꢀdimethylꢀ4b,7,8,9ꢀtetrahydroꢀ6Hꢀdiꢀ
benzo[2,3:5,6][1,4]diazepino[7,1ꢀa]isoindoleꢀ5,15ꢀdione (5b)
was obtained from compound 3b (0.42 g, 1 mmol) and propionic
anhydride (2 mL) as described for the synthesis of compound 5a
(the amount of PriOH was 5 mL). The yield was 0.17 g (42%),
colorless solid, m.p. 242—245 °C (from MeCN). Found (%):
C, 71.13; H, 6.21; N, 7.15. C24H24N2O4. Calculated (%):
C, 71.27; H, 5.98; N, 6.93. IR, ν/cm–1: 3284, 3230 (NH), 1678,
1630 (CO), 1611, 1586, 1536, 1511, 1499 (arom.). 1H NMR
(CDCl3), δ: 0.71, 0.97 (both s, 6 H, Me); 1.90—2.50 (m, 4 H, CH2);
3.91, 4.10 (both s, 6 H, OMe); 5.96 (s, 1 H, CH); 6.70—7.10 (m, 5 H,
NH, CH arom.); 7.55 (dd, 1 H, CH arom., 3J = 7.8 Hz, 4J= 1.2 Hz);
7.59 (d, 1 H, CH arom., J = 8.7 Hz). MS, m/z: 404 [M]+.
Xꢀray diffraction study of compounds 3b and 5a. Their single
crystals suitable for Xꢀray diffraction were grown by slow evapoꢀ
ration of the corresponding solutions in acetonitrile.
Experimental reflection intensities were measured on
a SMART APEX2 CCD diffractometer (λ(MoꢀKα) = 0.71073 Å,
graphite monochromator, ω scan mode). The initial intensity
reflection arrays were processed with the APEX2 program packꢀ
age.9 The structures were solved by the direct methods and reꢀ
fined by the fullꢀmatrix leastꢀsquares method in the anisotropic
approximation for the nonꢀhydrogen atoms on F2hkl. The hyꢀ
drogen atoms were located geometrically, except for the H atoms
at oxygen and nitrogen, which were located from the difference
electronꢀdensity maps and normalized to distances of 0.85 (for O)
and 0.90 Å (for N). All the H atoms were refined using a riding
model (Uiso(H) = nUeq(C,O,N), where n = 1.5 for the methyl
C atoms and the O atoms and n = 1.2 for the other C atoms and
the N atoms). The structures were solved and refined with the
SHELXTL program.10 The crystallographic parameters and the
data collection statistics are given in Table 2.
Compound
3b
5a
Molecular formula
Molecular weight
Crystal color
Crystal shape
Crystal dimensions/mm
T/K
Crystal system
Space group
a/Å
C26H29N3O5
463.52
Colorless
Plates
C26H29N3O5
463.52
Colorless
Prisms
0.22×0.16×0.02 0.15×0.10×0.10
100(2)
Orthorhombic
Pca21
18.693(5)
12.136(3)
11.102(3)
90
2518.5(11)
4
1.222
100(2)
Monoclinic
Pn
6.8450(9)
11.4650(14)
11.4815(15)
105.486(3)
868.33(19)
2
b/Å
c/Å
β/deg
3
V/Å
Z
dcalc/g cm–3
1.317
Absorption coefficient
μ/mm–1
0.086
0.085
F(000)
984
364
θ scan range/deg
Number of measured
reflections
1.68—27.00
16655
1.78—29.00
10124
Number of independent
reflections
2891
2313
Rint
0.1051
312
2104
0.0731
237
1814
Number of parameters refined
Number of reflections
with I ≥ 2σ(I)
Scan completeness (%)
GOOF
99.8
1.011
0.0470
99.7
1.071
0.0457
References
R1(F)* for reflections
with I ≥ 2σ(I))
1. L. Yu. Ukhin, K. Yu. Suponitskii, L. V. Belousova, Zh. I.
Orlova, Izv. Akad. Nauk, Ser. Khim., 2009, 2399 [Russ. Chem.
Bull., Int. Ed., 2009, 58, 2478].
wR2(F2)** for all reflections
Residual electron
0.1025
0.276/–0.226
0.0959
0.255/–0.246
–3
density (max/min)/e Å
2. L. Yu. Ukhin, K. Yu. Suponitskii, T. N. Gribanova, L. V.
Belousova, E. N. Shepelenko, Izv. Akad. Nauk, Ser. Khim.,
2010, 1000 [Russ. Chem. Bull., Int. Ed., 2010, 59, 1023].
3. L. Yu. Ukhin, E. N. Shepelenko, L. V. Belousova, Zh. I.
Orlova, G. S. Borodkin, K. Yu. Suponitskii, Izv. Akad. Nauk, Ser.
Khim., 2011, 345 [Russ. Chem. Bull., Int. Ed., 2011, 60, 352].
4. S. Miyano, N. Abe, Chem. Pharm. Bull., 1972, 20, 1588.
5. S. Miyano, Japan Kokai, 1974, 495944.
6. Y. Tamura, L. Chen, M. Fujita, Y. Kita, J. Heterocycl. Chem.,
1980, 17, 1.
7. M. del R. Arellano, R. Martinez, E. Cortes, J. Heterocycl.
Chem., 1982, 19, 321.
* R1 = ∑|Fo – |Fc||/∑(Fo).
** wR2 = ∑[w(Fo – Fc ) ]/∑[w(Fo ) ]
2
2 2
2 2 1/2
.
pound 3a (0.72 g, 2 mmol) and Ac2O (2.5 mL) was heated to
homogenization, refluxed for 1 min, and cooled to room temꢀ
perature. Then PriOH (3 mL) was added and the mixture was
cooled with ice water. The precipitate that formed was filtered
off, washed with cold PriOH and light petroleum, and dried.
The yield of compound 5a was 0.31 g (46%), colorless solid, m.p.
280—284 °C (from MeCN). Found (%): C, 76.94; H, 6.05;
N, 8.23. C22H20N2O2. Calculated (%): C, 76.72; H, 5.85; N, 8.13.
IR, ν/cm–1: 3308, 3240 (NH), 1682, 1624 (CO), 1596, 1501
8. Int. Pat. Appl. WO 2007026024; Chem. Abstrs, 2007, 146,
316950.
9. APEX2 and SAINT, Bruker AXS Inc., 2005, Madison, Wisꢀ
consin, USA.
1
(arom.). H NMR (CDCl3), δ: 0.67, 1.01 (both s, 6 H, Me);
1.90—2.50 (m, 4 H, CH2); 6.10 (s, 1 H, CH); 6.60—7.20 (m, 4 H,
NH, CH arom.); 7.38 (dd, 1 H, CH arom., 3J = 7.8 Hz, 4J = 1.2 Hz);
7.55, 7.95 (both m, 4 H, CH arom.).
10. G. M. Sheldrick, Acta Crystallogr., 2008, A64, 112.
B. Compound 5a was also obtained in a similar way from
compound 3a (0.34 g, 0.9 mmol) and propionic anhydride (2 mL).
The yield was 0.21 g (65%).
Received December 7, 2010;
in revised form February 24, 2011