Preparation of perinones via a novel multicomponent synthesis of isoindole scaffold

Article abstract of DOI:10.1016/j.tet.2011.05.078

A convenient procedure for the preparation of isoindole derivatives is described. The method is based on the multicomponent reaction of heterocyclic ketene aminals with dialkyl acetylenedicarboxylates in presence of DMAP. The reaction is very simple from

Full text of DOI:10.1016/j.tet.2011.05.078

Tetrahedron 67 (2011) 5409e5414
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Preparation of perinones via a novel multicomponent synthesis of isoindole
scaffold
a
a
,
b
€
_
*
€
S¸ evket Hakan Ungoren , Irfan Koca , Filiz Yilmaz
a Department of Chemistry, Faculty of Arts and Sciences, Bozok University, 66200 Yozgat, Turkey
b Department of Chemistry, Faculty of Arts and Sciences, Anadolu University, 26470 Eskis¸ehir, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
A convenient procedure for the preparation of isoindole derivatives is described. The method is based on
the multicomponent reaction of heterocyclic ketene aminals with dialkyl acetylenedicarboxylates in
presence of DMAP. The reaction is very simple from an experimental point of view and allows the cre-
ation of a fused isoindole moiety with concomitant formation of benzene and pyrrole ring in a single
operation.
Received 10 February 2011
Received in revised form 25 April 2011
Accepted 16 May 2011
Available online 25 May 2011
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Heterocyclic ketene aminals
Multicomponent reactions
Perinones
Isoindolo[2,1-a]perimidin-12-one
Cl
Cl
1. Introduction
Cl
Cl
The isoindole moiety has become attractive targets in organic
and medicinal chemistry. This heterocyclic framework is an integral
part of the structure of some biologically active compounds,1 dyes
and pigments2 and a few alkaloids.3 Moreover; isoindoles have
been widely used for their fluorescent and electroluminescent
properties, which make them attractive candidates for organic
light-emitting devices.4
O
O
O
N
N
N
N
N
N
HN
OH
Although, the synthesis of heterocycles functionalized with
isoindole unit is clearly underdeveloped, recent progress in syn-
thetic organic chemistry has led to the development of new
methods for the preparation of diversely substituted isoindoles.5
Perinones, fused perimidine compounds of isoindoles, are used
as dyes and pigments recommended for a wide range of industrial
plastics. They exhibit shades of colour from red to orange, for
example, SR 60 and SR 135 are commercial perinone dyes. More-
over SR 180 has been desired with superior heat stability and
strength compared to the others perinone dyes.6 According to
literature, these dyes are usually constructed via harsh conditions
starting from naphthalene-1,8-diamine and phthalic anhydride
derivatives.2d,7
Solvent Red 180
Solvent Red 135
Solvent Orange 60
potential for the synthesis of a wide variety of heterocyclic and
fused heterocyclic compounds.8,9 Literature survey revealed that
multicomponent reactions (MCRs) constitute an especially attrac-
tive synthetic strategy, since they provide easy and rapid access to
large libraries of organic compounds with diverse substitution
patterns and there are few reports about MCRs of HKAs connotating
that reaction of aldehydes and active methylene compounds with
HKAs to give pyridinone8b and naphthpyridine10 derivatives.
As part of our current studies on the MCRs to synthesize novel
functional heterocycles,11 we report herein a facile multicompo-
nent synthesis of isoindoles fused perimidine via the reaction be-
tween 2-acylmethylene substituted perimidines as HKAs and
dialkyl acetylenedicarboxylates (DAAC) in the presence of dimethyl
amino pyridine (DMAP).
As important intermediates, heterocyclic ketene aminals
(HKAs), also known as cyclic 1,1-enediamines, have shown great
* Corresponding author. Tel.: þ90 354 242 1021; fax: þ90 354 242 1022; e-mail
_
address: i_koca@yahoo.com (I. Koca).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.05.078

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S¸ .H. Ungoren et al. / Tetrahedron 67 (2011) 5409e5414
5410
2. Results and discussions
The 1H NMR spectrum of 5a showed three methoxy protons at
4.11, 4.02, 3.36 ppm, and a methyl proton at 2.84 ppm. The 13C
NMR showed four carbonyl carbons at 167.4, 165.9, 164.6 and
160.9 ppm, a methyl carbon at 15.7 ppm and three methoxy car-
bons at
53.4, 53.3, 53.1 ppm. In the 13C NMR spectra of 5a, new
d
The starting materials, 1H-perimidin-2(3H)-ylidenes (3a,b),
have been previously reported from the reactions of the corre-
sponding diketene or 3,3-dichloroacryloyl chloride with naphtha-
lene-1,8-diamine.12 However, compounds 3a,b and the new
derivatives 3c,d, have been prepared from 1 via a new method
d
d
aromatic carbon signals along with carbon signals of perimidine
moiety were clearly observed.
(Scheme 1) starting from the corresponding
b
-keto esters 2aed in
Unambiguous evidence for the structure of 5c was obtained by
using X-ray analysis (Fig. 1).13 The compound crystallizes in the
triclinic space group P-1. Dihedral angle between the isoindolo
plane [Cg1: N(2)eC(5)eC(6)eC(7)eC(13)eC(14)eC(15)eC(18)e
C(19)] and the perimidine plane [Cg2: N(2)eC(5)eN(1)eC(4)e
C(3)eC(2)eC(1)eC(20)eC(25)eC(24)eC(23)eC(22)eC(21)] is equal
to 3.93ꢀ, which indicates that the two ring systems are almost
coplanar. However, the isoindolo ring and the phenyl ring are not
coplanar, the dihedral angle being 59.89ꢀ.
A possible reaction scenario (outlined in Scheme 2) is as follows:
the tandem addition of a carbanion, generated from heterocyclic
ketene aminal by DMAP, to C^C bounds of two acetylenic esters,
would generate a species, which can transform into an aromatic
system well-disposed to undergo electrocyclization to afford
a dihydrobenzene derivative, and the latter would undergo de-
hydration to deliver polysubstituted phenyl ring. It is similar that
xylene at reflux in good yields (56e73%). Short reaction times
resulted in the isolation of significant amounts of the correspond-
ing amides together with the perimidines.
R1
O
O
O
R1
NH2 NH2
EtO
PTSA cat.
O
O
HN
NH
NH2 HN
+
Reflux
5 h., xylene
R1
1
2a-d
3a-d
2a, 3a: R1 = Me
2b, 3b: R1 = Ph
2c, 3c: R1 = 4-(MeO)Ph 2d, 3d: R1 = 3,4-(MeO)2Ph
Scheme 1. Synthesis of compound 3.
the formation of a phenyl ring from the MCR of b-keto esters with
Simply heating an EtOAc solution of HKAs (3), 2 equiv of DAAD,
and 1.2 equiv of DMAP led to the formation of 2-phenyl substituted
perimidine derivatives as intermediate products. Subsequent
intramolecular reaction of the intermediate products led to poly-
functionalized 8-alkyl-12-oxo-12H-isoindolo[2,1-a]perimidine-9,10,
11-tricarboxylate derivatives (5) in good yield (Table 1). In the event
that there is 1 equiv of DAAD used, the reactions gave the same
products. When MeCN was used as solvent, the final products were
obtained in similar yields. All crude products can be purified by
crystallization.
DMAP and DAAD was previously reported.14 Finally, the reaction is
completed with nucleophilic attack of an N-atom of perimidine ring
on the C]O of corresponding ester attached to phenyl ring.
3. Conclusion
In conclusion we have achieved an efficient process for the
synthesis of isoindolo[2,1-a]perimidin-12-one derivatives starting
from readily available reagents. The reaction is very simple from an
experimental point of view and allows the creation of a fused
Table 1
Synthesis of heterocyclic keten aminals 5aeh
COOR2
COOR2
R2OOC
R2OOC
R1
O
COOR2
COOR2
R2OOC
O
OR2
R1
R1
DMAP
HN
NH
2
+
reflux, 30 min
EtOAc
O
N
N
N
NH
O
OR2
4a,b
3a-d
5a-h
Entry
HKA
DAAD
Product
COOMe
COOMe
Recrystallization solvent
Yielda (%)
MeOOC
Me
O
OMe
1
3a
Acetonitrile
68
O
N
N
(5a)
OMe
OMe
O
O
COOMe
COOMe
MeOOC
N
2
3b
Acetonitrile
70
O
N
(5b)
OMe
O

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S¸ .H. Ungoren et al. / Tetrahedron 67 (2011) 5409e5414
5411
Table 1 (continued )
Entry
HKA
DAAD
Product
Recrystallization solvent
Acetonitrile
Yielda (%)
COOMe
MeOOC
O
OMe
OMe
OMe
COOMe
MeO
3
3c
75
O
N
N
(5c)
O
O
COOMe
MeOOC
COOMe
MeO
4
3d
Ethyl acetate
65
MeO
O
N
N
(5d)
OMe
OEt
O
O
COOEt
tEOOC
Me
COOEt
5
6
7
3a
3b
3c
Ethyl acetate
2-Propanol
2-Propanol
78
69
62
O
N
N
(5e)
OEt
OEt
O
O
COOEt
COOEt
tEOOC
N
O
N
(5f)
O
O
OEt
OEt
COOEt
COOEt
tEOOC
MeO
O
N
N
(5g)
O
O
OEt
OEt
COOEt
COOEt
tEOOC
N
MeO
MeO
8
3d
2-Propanol
72
O
N
(5h)
O
OEt
a
Isolated yield of analytically pure compound.
isoindole moiety with concomitant formation of benzene and
pyrrole ring in a single operation.
spectrometer using CDCl3 or DMSO-d6 solvents. The IR spectra were
obtained in potassium bromide pellets using a Jasco FTIR-460 Plus
spectrometer. Diffraction data for 5c were collected with a Bruker
AXS APEX15a CCD diffractometer. Diffraction data were collected
over the full sphere and were corrected for absorption. The crystal
structures were solved by direct methods and refined by using
SHELXS-97 and SHELXL-97 crystallographic software packages.15b,c
All nonhydrogen atoms were refined anisotropically using re-
flections I[2r (I). Hydrogen atoms were located in ideal positions.
Geometric calculations and visualizations were done using PLA-
TON,15d MERCURY.15e
4. Experimental
4.1. General
Melting points were measured on an Electrothermal 9100 ap-
paratus and uncorrected. Elemental analyses for C, H and N were
performed using a LECO-932 CHNS-O Elemental Analyzer. 1H and
13C NMR spectra were measured with Bruker Avance 400

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S¸ .H. Ungoren et al. / Tetrahedron 67 (2011) 5409e5414
5412
13C NMR (DMSO-d6): 191.5 (C]O),152.4 (C]CHCOMe), 135.1, 134.6,
134.2, 128.8, 128.7, 119.3, 118.7, 116.3, 105.8, 105.1 (C]C, aro.), 80.5
(C]CHCOMe), 29.0 ppm (CH3). Anal. Calcd for C14H12N2O: C, 74.98;
H, 5.39; N, 12.49. Found: C, 74.83; H, 5.33; N, 12.59%.
4.2.2. 2-(1H-Perimidin-2(3H)-ylidene)-1-phenylethanone
(3b). Brown crystals, yield: 0.172 g, 60%; mp 246 ꢀC. FT-IR (KBr): nmax
:
3295 (NH), 1649 (C]O), 1633 (C]C) cmꢁ1 1H NMR (DMSO-d6):
;
13.80, 10.73 (s, 2H, NH), 7.84e6.59 (m, 11H, AreH), 5.59 (s, 1H,]CH)
ppm; 13C NMR (DMSO-d6): 184.5 (C]O), 153.9 (C]CHCOPh), 140.5,
135.1, 134.7, 134.1, 130.9, 128.8, 126.6, 119.7, 119.0, 116.7, 106.2, 105.3
(C]C, aro.), 77.9 ppm (C]CHCOPh). Anal. Calcd for C19H14N2O: C,
79.70; H, 4.93; N, 9.78. Found: C, 79.84; H, 4.99; N, 9.61%.
4.2.3. 1-(4-Methoxyphenyl)-2-(1H-perimidin-2(3H)-ylidene)etha-
none (3c). Brown crystals, yield 0.193 g, 61%; mp 300 ꢀC. FT-IR
(KBr): nmax: 3290 (NH), 1647 (C]O), 1631 (C]C) cmꢁ1 1H NMR
;
(DMSO-d6): NH, not detected, 7.84e6.59 (m, 10H, AreH), 5.53 (s,
1H,]CH), 3.80 (s, 3H, OCH3); 13C NMR (DMSO-d6): 184.0 (C]O),
153.5 (C]CHCOPh), 161.6, 134.7, 132.9, 128.7, 128.4, 119.1, 116.5,
114.0, 105.6 (C]C, aro.), 77.1 ppm (C]CHCOPh), 55.7 (OCH3). Anal.
Calcd for C20H16N2O2: C, 75.93; H, 5.10; N, 8.86. Found: C, 75.81; H,
5.10; N, 8.72%.
4.2.4. 1-(3,4-Dimethoxyphenyl)-2-(1H-perimidin-2(3H)-ylidene)
ethanone (3d). Orange crystals, yield 0.253 g, 73%; mp 228 ꢀC. FT-IR
(KBr): nmax: 3332 (NH), 1621 (C]O) cmꢁ1 1H NMR (DMSO-d6):
;
Fig. 1. Molecular structure of 5c (Hydrogen atoms have been omitted for clarity).
R2OOC
COOR2
COOR2
COOR2
R1
N
R1
COOR2 R2OOC
R1
DMAP [DMAPH]+
O
O
O
COOR2
CH
O
COOR2
R1
H
NH
HN
NH
N
NH
N
NH
[DMAPH]+
DMAP
COOR2
COOR2
COOR2
R2OOC
COOR2
R2OOC
R1
COOR2
R2OOC
HO
COOR2
R1
COOR2
NH
COOR2
R1
H
O
- R2OH
- H2O
N
N
N
N
NH
Scheme 2. A proposed mechanism for the pseudomulticomponent reaction of HKAs.
4.2. General procedure for the preparation of 3
A solution of -keto ester 2 (1 mmol) and naphthalene-1,
8-diamine (1) (0.158 g, 1 mmol) in the presence of PTSA (catalytic
amount) in xylene (50 mL) was refluxed for 5 h. After removal of the
solvent, the residue was crystallized from xylene to give pure 3aed.
13.78, 10.65 (s, 2H, NH), 7.41e6.58 (m, 9H, AreH), 5.55 (s, 1H,]CH),
3.80 (s, 6H, 2ꢂ OCH3); 13C NMR (DMSO-d6): 184.0 (C]O),153.4 (C]
CHCOPh), 151.3, 148.8, 135.2, 134.7, 134.1, 133.1, 128.8, 126.4, 119.8,
119.5, 118.8, 116.5, 111.4, 109.9, 106.0, 105.2 (C]C, aro.), 77.2 ppm
(C]CHCOPh), 56.0, 55.7 (2ꢂ OCH3). Anal. Calcd for C21H18N2O3: C,
72.82; H, 5.24; N, 8.09. Found: C, 72.94; H, 5.19; N, 8.24%.
b
4.2.1. 1-(1H-Perimidin-2(3H)-ylidene)acetone (3a). Grey crystals,
yield 0.125 g, 56%; mp 260 ꢀC. FT-IR (KBr): nmax: 3124 (NH), 1658
(C]O), 1631 (C]C) cmꢁ1; 1H NMR (DMSO-d6): 13.33, 10.41 (s, 2H,
NH), 7.26e6.52 (m, 6H, AreH), 4.82 (s, 1H,]CH),1.91 ppm (COCH3);
4.3. General procedure for the preparation of products 5
To stirred solution of 3 (1 mmol) and the corresponding dialkyl
acetylenedicarboxylates (2 mmol) in EtOAc (30 mL) was added

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5413
dropwise DMAP (1.2 mmol) in EtOAc (10 mL), and the mixture was
stirred at rt for 1 min. Later the mixture was heated at reflux for
30 min. The solvent was removed under reduced pressure, and the
residue was treated with the petroleum ether to give correspond-
ing products 5, which were filtered off and recrystallized from the
proper solvent and dried (P2O5).
NMR (CDCl3): 8.50e6.91 (m, 11H, AreH), 4.62, 4.42, 4.05 (3ꢂ q,
J¼7.2 Hz, 6H, OCH2), 1.51, 1.39, 0.98 ppm (3ꢂ t, J¼7.2 Hz, 9H, Me);
13C NMR (CDCl3): 166.3, 165.3, 164.2, 160.9 (C]O), 146.2, 140.5,
138.7, 138.5, 133.8, 133.7, 132.0, 131.4, 131.2, 130.1, 129.5, 128.6, 127.9,
127.7, 127.7, 127.5, 126.5, 123.6, 123.4, 118.2, 110.5 (AreC]C, C]N),
62.8, 62.6, 61.9 (3ꢂ OCH2), 14.0, 13.8, 13.5 ppm (3 Me). Anal. Calcd
for C33H26N2O7 (563 g/mol): C, 70.45; H, 4.66; N, 4.98. Found: C,
70.53; H, 4.56; N, 5.05%.
4.3.1. Trimethyl 8-methyl-12-oxo-12H-isoindolo[2,1-a]perimidine-9,10,
11-tricarboxylate (5a). Red crystals, yield 0.313 g, 68%; mp 249 ꢀC.
FT-IR (KBr): nmax: 1721 (br, C]O), 1639 (C]N) cmꢁ1
;
1H NMR
4.3.7. Triethyl 8-(4-methoxyphenyl)-12-oxo-12H-isoindolo[2,1-a]peri-
midine-9,10,11-tricarboxylate (5g). Red crystals, yield 0.367 g, 62%;
mp 117 ꢀC. FT-IR (KBr): nmax: 1721 (br, C]O), 1638 (C]N) cmꢁ1; 1H
NMR (CDCl3): 8.50e6.99 (m, 10H, AreH), 3.93 (s, 3H, OMe),
4.61, 4.41, 4.09 (3ꢂ q, J¼7.2 Hz, 6H, OCH2), 1.50, 1.39, 1.04 ppm (3ꢂ t,
J¼7.2 Hz, 9H, Me); 13C NMR (CDCl3): 166.5, 165.3, 164.2, 160.9
(C]O), 160.0, 146.3, 140.8, 138.7, 138.6, 133.7, 132.1, 131.4, 131.0,
131.0, 130.1, 127.9, 127.7, 126.5, 126.0, 123.7, 123.4, 118.2, 113.0, 110.5
(AreC]C, C]N), 62.8, 62.7, 61.9 (3ꢂ OCH2), 55.4 (OMe), 14.0, 13.8,
13.7 ppm (3ꢂ Me). Anal. Calcd for C34H28N2O8 (593 g/mol): C,
68.91; H, 4.76; N, 4.73. Found: C, 69.00; H, 4.76; N, 4.89%.
(CDCl3): 8.39e7.27 (m, 6H, AreH), 4.11, 4.02, 3.96 (3ꢂ s, 9H, OMe),
2.84 ppm (s, 3H, AreMe); 13C NMR (CDCl3): 167.4, 165.9, 164.6,
160.9 (C]O), 147.4, 140.2, 138.5, 136.7, 133.6, 132.0, 131.1, 129.4,
129.4, 128.0, 127.8, 127.6, 126.6, 123.5, 123.4, 117.9, 110.4 (AreC]C,
C]N), 53.4, 53.3, 53.1 (3ꢂ OMe), 15.7 ppm (Me). Anal. Calcd for
C25H18N2O7 (458 g/mol): C, 65.50; H, 3.96; N, 6.11. Found: C, 65.24;
H, 3.87; N, 6.13%.
4.3.2. Trimethyl 12-oxo-8-phenyl-12H-isoindolo[2,1-a]perimidine-9,
10,11-tricarboxylate (5b). Red crystals, yield 0.365 g, 70%; mp
275 ꢀC. FT-IR (KBr): nmax: 1741,1728,1714 (C]O),1644 (C]N) cmꢁ1
;
1H NMR (DMSO-d6): 8.34e6.76 (m, 11H, AreH), 4.00, 3.88,
3.52 ppm (3ꢂ s, 9H, OMe); 13C NMR (DMSO-d6): 166.5, 165.6, 165.0,
160.6 (C]O), 144.2, 143.4, 139.3, 138.7, 138.6, 133.9, 123.0, 129.9,
129.8, 129.1, 128.7, 128.5, 128.4, 127.9, 126.6, 123.6, 123.1, 118.1, 116.2,
110.1, 109.9 (AreC]C, C]N), 54.3, 53.7, 53.2 ppm (3ꢂ OMe). Anal.
Calcd for C30H20N2O7 (520 g/mol): C, 69.23; H, 3.87; N, 5.38. Found:
C, 69.53; H, 4.16; N, 5.15%.
4.3.8. Triethyl 8-(3,4-dimethoxyphenyl)-12-oxo-12H-isoindolo[2,1-a]
perimidine-9,10,11-tricarboxylate (5h). Red crystals, yield 0.448 g,
72%; mp 90 ꢀC. FT-IR (KBr): nmax: 1722 (br, C]O),1641 (C]N) cmꢁ1
;
1H NMR (CDCl3): 8.54e6.90 (m, 9H, AreH), 4.61, 4.41, 4.14 (3ꢂ q,
J¼7.2 Hz, 6H, OCH2), 4.01, 3.88 (2ꢂ s, 6H, 2 OMe), 1.50, 1.39,
1.04 ppm (3ꢂ t, J¼7.2 Hz, 9H, Me); 13C NMR (CDCl3): 166.6, 165.3,
164.2, 161.0 (C]O), 149.5, 148.1, 140.7, 138.6, 133.7, 131.9, 131.4,
128.0, 127.8, 126.5, 126.1, 123.7, 123.4, 122.1, 113.7, 110.5, 110.2
(AreC]C, C]N), 62.8, 62.6, 61.9 (3ꢂ OCH2), 56.0, 56.0 (2ꢂ OMe),
14.0, 13.8, 13.7 ppm (3ꢂ Me). Anal. Calcd for C35H30N2O9 (623 g/
mol): C, 67.52; H, 4.86; N, 4.50. Found: C, 67.26; H, 4.72; N, 4.39%.
4.3.3. Trimethyl 8-(4-methoxyphenyl)-12-oxo-12H-isoindolo[2,1-a]
perimidine-9,10,11-tricarboxylate (5c). Red crystals, yield 0.414 g,
75%; mp 211 ꢀC. FT-IR (KBr): nmax: 1741, 1718 (C]O), 1641 (C]N)
cmꢁ1; 1H NMR (CDCl3): 8.39e6.93 (m, 10H, AreH), 4.14, 3.95, 3.94,
3.36 ppm (4ꢂ s, 12H, OMe); 13C NMR (CDCl3): 161.0, 165.9, 164.5,
160.7 (C]O), 160.0, 146.0, 140.7, 138.9, 138.4, 133.5, 132.1, 131.1,
130.9,130.6,129.5,127.9,127.8,127.7,126.5,125.7,123.7,123.4,118.0,
113.0, 110.5 (AreC]C, C]N), 55.4, 53.5, 53.4, 52.7 ppm (4ꢂ OMe).
Anal. Calcd for C31H22N2O8 (551 g/mol): C, 67.63; H, 4.03; N, 5.09.
Found: C, 67.44; H, 3.89; N, 5.17%.
Acknowledgements
We wish to dedicate this article to the deceased Prof. Dr. Yunus
AKC¸ AMUR. The authors are grateful to The Medicinal Plants and
Medicine Research Centre of Anadolu University for the use of the
X-ray diffractometer. This study was financially supported by The
€ _
Scientific and Technological Research Council of Turkey (TUBITAK),
4.3.4. Trimethyl 8-(3,4-dimethoxyphenyl)-12-oxo-12H-isoindolo[2,1-
project No: TBAG 110T033.
a]perimidine-9,10,11-tricarboxylate (5d). Red crystals, yield 0.378 g,
65%; mp 228 ꢀC. FT-IR (KBr): nmax: 1727 (C]O), 1638 (C]N) cmꢁ1
;
Supplementary data
1H NMR (CDCl3): 8.54e6.93 (m, 9H, AreH), 4.14, 4.01, 3.96, 3.88,
3.66 ppm (5ꢂ s, 15H, OMe); 13C NMR (CDCl3): 167.0, 165.9, 164.5,
160.9 (C]O), 149.5, 148.1, 146.2, 140.6, 138.8, 138.5, 133.7, 132.1,
131.3, 130.7, 129.8, 128.0, 127.8, 126.7, 125.8, 123.8, 123.6, 122.0,
118.2, 113.6, 110.6, 110.2 (AreC]C, C]N), 56.0, 55.9, 53.5, 53.5,
52.8 ppm (5ꢂ OMe). Anal. Calcd for C32H24N2O9 (581 g/mol): C,
66.20; H, 4.17; N, 4.83. Found: C, 66.29; H, 4.24; N, 4.67%.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tet.2011.05.078.
References and notes
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4.3.5. Triethyl 8-methyl-12-oxo-12H-isoindolo[2,1-a]perimidine-9,10,
11-tricarboxylate (5e). Red crystals, yield 0.390 g, 78%; mp 205 ꢀC.
FT-IR (KBr): nmax: 1734, 1723 (C]O), 1637 (C]N) cmꢁ1 1H NMR
;
(DMSO-d6): 8.28e7.35 (m, 6H, AreH), 4.43, 4.38, 4.33 (3ꢂ q,
J¼7.2 Hz, 6H, OCH2), 1.37, 1.29, 1.19 (3ꢂ t, J¼7.2 Hz, 9H, 3ꢂ Me),
2.79 ppm (s, 3H, AreMe); 13C NMR (DMSO-d6): 166.5, 165.0, 164.8,
160.2 (C]O), 147.7, 140.2, 138.9, 136.7, 133.9, 131.1, 130.6, 129.5,
129.4, 128.5, 127.8, 127.7, 126.6, 123.5, 123.2, 118.0, 109.7 (AreC]C,
C]N), 63.2, 62.7, 62.5 (3ꢂ OCH2), 15.8 (AreMe), 14.3, 14.3, 14.1 ppm
(3ꢂ Me) Anal. Calcd for C28H24N2O7 (500 g/mol): C, 67.19; H, 4.83;
N, 5.60. Found: C, 67.27; H, 4.83; N, 5.51%.
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9,10,11-tricarboxylate (5f). Red crystals, yield 0.389 g, 69%; mp
185 ꢀC. FT-IR (KBr): nmax: 1741, 1719 (C]O), 1640 (C]N) cmꢁ1 1H
12-oxo-8-phenyl-12H-isoindolo[2,1-a]perimidine-
;

€
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