Facile synthesis of 1,8-naphthalimides in palladium-catalysed aminocarbonylation of 1,8-diiodo-naphthalene

Article abstract of DOI:10.1016/j.tet.2007.10.026

1,8-Diiodo-naphthalene was aminocarbonylated with various primary and secondary amines in the presence of palladium(0) complexes formed in situ from palladium(II) acetate and triphenylphosphine. In the case of primary amines, depending on the amine to substrate ratio, two types of products have been obtained in highly chemoselective reaction: dicarboxamides and N-substituted imides have been formed at high and low amine to substrate ratio, respectively. The reaction tolerates the ester functionality, so that amino acid esters could serve as N-nucleophiles and in this way, naphthalimides possessing stereogenic centre in the N-substituent could be synthesised.

Full text of DOI:10.1016/j.tet.2007.10.026

Available online at www.sciencedirect.com
Tetrahedron 64 (2008) 983–987
Facile synthesis of 1,8-naphthalimides in palladium-catalysed
aminocarbonylation of 1,8-diiodo-naphthalene
ꢀ
*
Attila Tak ꢀa cs, P ꢀe ter Acs and L ꢀa szl ꢀo Koll ꢀa r
Department of Inorganic Chemistry, University of Pe´cs, H-7624 Pe´cs, PO Box 266, Hungary
Received 14 September 2007; revised 2 October 2007; accepted 4 October 2007
Available online 7 October 2007
Dedicated to Professor Csaba Sz ꢀa ntay on the occasion of his 80th birthday
Abstract—1,8-Diiodo-naphthalene was aminocarbonylated with various primary and secondary amines in the presence of palladium(0) com-
plexes formed in situ from palladium(II) acetate and triphenylphosphine. In the case of primary amines, depending on the amine to substrate
ratio, two types of products have been obtained in highly chemoselective reaction: dicarboxamides and N-substituted imides have been formed
at high and low amine to substrate ratio, respectively. The reaction tolerates the ester functionality, so that amino acid esters could serve as
N-nucleophiles and in this way, naphthalimides possessing stereogenic centre in the N-substituent could be synthesised.
Ó 2007 Elsevier Ltd. All rights reserved.
1. Introduction
investigating parallel and perpendicular stacking of ferro-
cene rings attached to a sterically desired backbone. The
7
The carbonylation of iodoaromatics and their synthetic ana-
logues in homogeneous catalytic reactions is well-known for
same homogeneous catalytic reaction was used for the cou-
pling of 1,8-diiodo-naphthalene with ruthenocenyl-dioxa-
borolane, resulting in ruthenoceno[a]acenaphthylene of
1
,2
the wide audience of chemists. By using various amines
and alcohols as N- and O-nucleophiles, carboxamides/keto-
carboxamides and esters/ketoesters can be synthesised in
8
peculiar redox behaviours.
3
aminocarbonylation and alkoxycarbonylation, respectively.
One type of the title compounds, N-alkyl-1,8-naphthalimide
derivatives, has been known as fluorosensors and their spec-
tral-luminescent characteristics have been studied in detail.
Several derivatives functionalised at the 4 and 5 positions
have been synthesised by conventional synthetic proce-
There are several applications concerning the synthesis of
simple building blocks and the functionalisation of biologi-
cally important skeletons as well.
4
9
–11
12
The palladium-catalysed homogeneous catalytic reaction
might be especially efficient in those cases where the target
carboxamides are hardly available via the conventional carb-
oxylic acid—carboxylic halide—carboxamide pathway
dures
coupling reactions. N-Phenyl- and N-benzyl-1,8-naphtha-
and palladium-catalysed Sonogashira and Stille
1
3
limide have been synthesised by the conventional reaction
of 1,8-naphthalene-dicarboxylic anhydride and aniline
1
4,15
1
4
(
e.g., with bulky substituents at the amide nitrogen). We
and benzylamine, respectively. N-Phenyl-imide can also
be obtained by the phenylation of 1,8-naphthalimide by
extended this methodology to the application of various
amino acid esters as N-nucleophiles. It has to be noted that
although the N-acylation of amino acids is widely used in
synthetic chemistry, the sporadic results have been published
for the use of amino acid derivatives for the introduction of
1
6
phenyl-boronates or by the phenylation of N-Br-1,8-naph-
thalimide.
1
7
Encouraged by the increasing importance of various
N-substituted imides serving as intermediates for the synthe-
5
,6
a carboxamide moiety.
1
8
sis of substituted heterocycles, especially those possessing
protected amino acid derivatives, we decided to investigate
the possibility of extending the scope of the aminocarbonyl-
ation methodology to novel type of ‘double acylation’ of the
amino functionality of amino acid esters by highly reactive
palladium-acyl intermediates. Accordingly, two types of
aminocarbonylation of 1,8-diiodo-naphthalene leading to
N-substituted carboxamides and imides are published in
the present paper.
Among the iodoaromatics, 1,8-diiodo-naphthalene was also
used as a substrate in some homogeneous catalytic reactions.
It was reacted with an appropriate ferrocenyl substituted
boroxin derivative in Suzuki coupling with the aim of
Keywords: Iodoaromatics; Aminocarbonylation; Carbon monoxide; Palla-
dium; Amine; Carbonylation.
*
Corresponding author. E-mail: kollar@ttk.pte.hu
0
040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.10.026

984
A. Tak aꢀ cs et al. / Tetrahedron 64 (2008) 983–987
2
. Results and discussion
CO, H NR
2
Pd(OAc)2 / PPh3
1
,8-Diiodo-naphthalene (1), synthesised from 1,8-diamino-
1
9
I
I
N
R
3
O
O
naphthalene, was reacted with carbon monoxide and
various amines such as tert-butylamine (a), aniline (b),
piperidine (d) and morpholine (e) (Scheme 1). Carrying out
the reaction in an amine excess (amine to 1 ratio of up to
3
were obtained as major products. Furthermore, as previously
1
R
a
b
c
t-Bu
Ph
/1), 1,8-dicarboxamides (2d, 2e) of expected structure
CH Ph
2
2
0
observed with aryl iodides, the reaction is accompanied by
the formation of compounds possessing both carboxamide
f
CH COOCH
2 3
g
h
CH(CH )COOCH
3 3
CH(CH(CH3)2)COOCH3
0
0
and ketocarboxamide functionalities (2 d, 2 e) due to partial
double carbon monoxide insertion (Table 1). By using 1,8-
diiodo-napthalene as a substrate, the chemoselectivity is
strongly dependant on the carbon monoxide pressure. Unlike
the simple iodoarenes, ketocarboxamides have been formed
in traces only under atmospheric carbon monoxide pressure,
i.e., the corresponding dicarboxamides could be isolated in
excellent yields. However, the unsymmetrically substituted
naphthalenes possessing both carboxamide and glyoxylamide
functionalities have been observed in comparable amount to
dicarboxamides (2d, 2e) under 40 bar carbon monoxide
pressure. The lack of the selective formation of bis(ketocar-
boxamides), i.e., the double insertion of carbon monoxide
into both iodoarene moieties of the starting material can be
explained by the steric reasons. The use of the primary
amines, tert-butylamine (a), aniline (b) and benzylamine
Scheme 2. Synthesis of N-substituted 1,8-naphthalimides in palladium-
catalysed aminocarbonylation of 1.
Reducing the amine to 1 ratio to nearly 1/1, various
N-substituted 1,8-naphthalimides with unfunctionalised
amines (3b, 3c) and those with the ester functionality (3f–
h) were obtained in highly chemoselective reaction in the
presence of simple primary amines (b, c) and amino acid
methylesters with NH termini (f–h), respectively (Scheme
3
2
2
). To the best of our knowledge, no imide formation has
been observed in aminocarbonylation reaction by using
either diiodoaromatics, bis(iodoalkenes), with sterically ap-
propriate structure or their corresponding triflate analogues.
In order to achieve yields of synthetic interest, the reaction
had to be conducted under 40 bar carbon monoxide pressure
in elevated reaction times (Table 2).
(
c) resulted in the corresponding carboxamides (2a–2c) in
traces only. The ring-closure products 3a–3c have been ob-
tained in these cases (vide infra) (Scheme 2). Only 3b and 3c
could be isolated in acceptable yield. The tert-butyl ana-
logue 3a underwent decomposition during isolation and
work-up, resulting in a rather complicated mixture contain-
ing the corresponding anhydride, acid and amide derivatives.
A side reaction leading to naphthalene-1,8-dicarboxylic an-
hydride was observed when amines of low reactivity were
used in the aminocarbonylation reaction. In the presence
of traces of water in the solvent (and even the adsorbed
water on the wall of the glass flask), the palladium-acyl
CO, HNR'R''
+
Table 2. Synthesis of 1,8-naphthalimides in palladium-catalysed amino-
carbonylation of 1
Pd(OAc)2 / PPh3
a
O
I
I
O
O
b
Isolated yield (imide) [%]
R'R"N
O
NR'R"
R'R"N
O
Amine
Reaction time [h]
NR'R"
t
1
2
2'
BuNH
(a)
(b)
42
42
42
90
90
90
0 (3a)
80 (3b)
82 (3c)
77 (3f)
78 (3g)
69 (3h)
2
PhNH
PhCH
GlyOMe (f)
AlaOMe (g)
ValOMe (h)
2
R'
R''
2
2
NH (c)
a
b
d
e
H
H
t-
Ph
-(CH ) -
2
5
a
-(CH ) O(CH ) -
2
2
2 2
Reaction conditions: 0.025 mmol Pd(OAc)
,8-diiodo-naphthalene (1), 0.55 mmol amine (b, c, f–h), 10 ml DMF,
40 bar CO.
2 3
, 0.05 mmol PPh , 0.5 mmol
1
Scheme 1. Synthesis of 1,8-naphthalene-dicarboxamides in palladium-
catalysed aminocarbonylation of 1.
b
Practically, complete conversion (>98%) has been obtained in all cases.
a
Table 1. Synthesis of dicarboxamides in palladium-catalysed aminocarbonylation of 1
b
b
Amine
Reaction time [h]
p(CO) [bar]
Yield/isolated yield
1,8-diamide) [%]
Yield/isolated yield
(1-amide-8-ketoamide) [%]
(
t
c
0
0
0
0
0
0
0
BuNH
2
(a)
Aniline (b)
22
22
22
24
24
66
66
40
1
40
1
40
1
40
20/0 (3a)
0 (2 a)
0 (2 b)
d
>98/75 (3b)
>98/72 (3b)
>99/85 (2d)
78/70 (2d)
>99/87 (2e)
63/50 (2e)
d
Aniline (b)
0 (2 b)
<1 (2 d)
Piperidine (d)
Piperidine (d)
Morpholine (e)
Morpholine (e)
22/15 (2 d)
<1 (2 e)
37/25 (2 e)
a
2 3
Reaction conditions: 0.025 mmol Pd(OAc) , 0.05 mmol PPh , 0.5 mmol 1,8-diiodo-naphthalene (1), 3.0 mmol a (2 mmol b, 1.5 mmol d, e), 10 ml DMF.
b
c
d
Practically, complete conversion (>98%) has been obtained in all cases.
Naphthalene-1,8-dicarboxylic anhydride was isolated.
The corresponding ring-closure products (N-substituted naphthalimides) have been formed exclusively.

A. Tak aꢀ cs et al. / Tetrahedron 64 (2008) 983–987
985
3
O
N
R
O
2
1
Et NHI
3
R'R"N(O)C
C(O)NR'R"
I
I
Et N
3
2
Et NHI
3
2
PdLn
2
Et N
3
2
R'R"NH
O
n-2
C(O)NHR
L
IPd
C
O
A
O
Ln-2IPd
PdILn-2
Ln-2IPd
PdILn-2
Et NHI
3
CO
Et N
3
RNH2
Ln-2I(CO)Pd Pd(CO)ILn-2
B
Scheme 3. The formation of 2 and 3 rationalised by a simplified reaction mechanism.
intermediate (C, vide infra, Scheme 3) undergoes hydrolysis
leading to the corresponding anhydride. The amount of
anhydride can be substantially decreased by using flame-
dried apparatus. It has to be noted that similar side reaction
providing carboxylic acid and anhydride has been observed
positions, with the same amino group. The high chemoselec-
tivity, the easy work-up of the reaction mixtures, as well as
the high functional group tolerance of aminocarbonylation,
regarding functional groups both at the N-alkyl substituent
and at the aryl moieties, make these reactions of synthetic
importance.
2
1
with 17-iodo-androst-16-ene derivatives as well.
The formation of the above products can be rationalised on
the basis of the following simplified reaction mechanism
4. Experimental
(
of 1 to palladium(0) complexes (PdL , where L stands for
Scheme 3). The oxidative addition of the iodoaryl bond
4.1. General procedures
n
triphenylphosphine and solvent donor ligands), formed in
situ from palladium(II) acetate and triphenylphosphine,
resulted in the corresponding bis(palladium-aryl) catalytic
intermediate (A). It is followed by carbon monoxide activa-
tion yielding a complex with terminal carbonyl ligand (B)
and its insertion into palladium–aryl bond results in the cor-
responding bis(palladium-acyl) complex (C). This catalytic
intermediate could react with a primary amine in two ways:
1
13
H and C NMR spectra were recorded in CDCl on a Varian
3
Inova 400 spectrometer at 400.13 and 100.62 MHz, respec-
tively. Chemical shifts d are reported in parts per million
relative to CHCl (7.26 and 77.00 ppm for H and C, re-
3
spectively). Elemental analyses were carried out on a 1108
Carlo Erba apparatus. Samples of the catalytic reactions
were analysed with a Hewlett Packard 5830A gas chromato-
graph fitted with a capillary column coated with OV-1.
1
13
(
acyl moieties react independently resulting in dicarbox-
i) by using the amine in 3-fold (or larger) excess, the two
0
amides (2) (or 2 by double carbon monoxide insertion)
1,8-Diiodo-naphthalene was synthesised as described previ-
1
9
and (ii) by using the substrate and amine in equimolar
amount, both acyl moieties react with the same N-nucleo-
phile yielding imides (3).
ously. The amines were purchased from Aldrich and were
used without any further purification. Solvents were dried
and purified by generally used procedures.
3. Conclusions
4.2. Aminocarbonylation experiments towards 1,8-
naphthalene-dicarboxamides at normal pressure
The palladium-catalysed aminocarbonylation of 1,8-diiodo-
naphthalene can be carried out in high isolated yields.
While the application of secondary amines resulted in the
formation of 1,8-dicarboxamides as major products and
In a typical experiment a solution of Pd(OAc) (5.6 mg,
2
0.025 mmol), PPh (13.1 mg, 0.05 mmol), 1,8-diiodo-naph-
3
thalene (1, 0.5 mmol) and primary or secondary amine (a–e,
1.5–3.0 mmol) (see Table 1) was dissolved in 10 ml DMF
under argon. Triethylamine (1.0 ml) was added to the homo-
geneous yellow solution and the atmosphere was changed to
carbon monoxide. The colour changed to dark red. The reac-
1
-amide-8-ketoamide derivatives as minor ones that of the
primary amines provided the corresponding N-substituted
,8-naphthalimides. The highly selective formation of the
1
latter products in a novel type of aminocarbonylation reac-
tion can be explained by the reaction of both palladium-
acyl moieties, situated in sterically highly favoured
ꢀ
tion was conducted for up to 66 h at 50 C. Some metallic
palladium was formed at the end of the reaction, which

986
A. Tak aꢀ cs et al. / Tetrahedron 64 (2008) 983–987
0 0
4.5.2. 1-[N,N-(Penta-1 ,5 -diyl)-carboxamido]-8-[N,N-
was filtered. (A sample of this solution was immediately
analysed by GC–MS.) The mixture was then concentrated
and evaporated to dryness. The residue was dissolved in
chloroform (20 ml) and washed with water (20 ml). The
organic phase was thoroughly washed twice with 5% HCl
0
NMR (CDCl ) d: 8.04–8.09 (m, 2H, Naph), 7.90 (dd, 7.0,
0
00
0
1
(penta-1 ,5 -diyl)-glyoxylamido]-naphthalene (2 d).
H
3
8.1 Hz, 1H, Naph), 7.50–7.56 (m, 3H, Naph), 3.30–4.02
(m, 8H, 4ꢁN(CH )), 1.45–1.85 (m, 12H, 6ꢁCH ).
1
3
C
NMR (CDCl ) d: 193.6, 170.9, 165.2, 135.5, 135.4, 134.8,
2
2
(
over Na SO and concentrated to a yellow waxy material
20 ml), saturated NaHCO (20 ml), brine (20 ml), dried
3
3
133.5, 130.9, 130.2, 128.4, 126.5, 125.9, 124.7, 49.3, 46.6,
42.5, 42.4, 26.2, 25.5, 25.4, 25.3, 24.7, 24.5. IR (KBr,
2
4
or a thick oil. Chromatography (silica, EtOAc/CHCl ¼1/9
3
ꢂ1
or silica, EtOAc/CHCl ¼1/1) yielded the desired dicarbox-
cm ): 1678 (CO), 1637 (br, 2ꢁCON). MS m/z (rel int.
3
0
amides (2d, 2e) or carboxamide–ketocarboxamides (2 d,
e), respectively.
%): 378 (2), 295 (6), 266 (100), 210 (18), 180 (15), 126
(11). Anal. Calcd for C H N O (378.47): C, 72.99; H,
0
2
2
2 26 2 3
6
EtOAc/CHCl ) 0.49; off-white solid, mp 136 C.
.92; N, 7.40. Found: C, 72.88; H, 6.75; N, 7.22. R (30%
f
ꢀ
4
1
.3. Aminocarbonylation experiments towards
,8-naphthalene-dicarboxamides at high pressure
3
0 0 0
.5.3. 1,8-Bis[N,N-(3 -oxa-penta-1 ,5 -diyl)-carboxami-
do]-naphthalene (2e). H NMR (CDCl ) d: 7.92 (d,
4
1
The DMF solution of the catalyst precursor and reactants
amounts given in Section 4.2) was transferred under argon
3
(
8.1 Hz, 2H, Naph), 7.46 (t, 7.0, 8.1 Hz, 2H, Naph), 7.38
(d, 7.0 Hz, 2H, Naph), 3.9 (m, 4H, 2NCH ), 3.85 (br s,
into a 100 ml stainless steel autoclave. The reaction vessel
was pressurised to 40 bar total pressure with carbon monox-
ide and the magnetically stirred mixture was heated in an oil
bath at 50 C for 24 h. The work-up procedure is identical
with that given above.
2
1
3
8H, 4ꢁCH ), 3.4–3.6 (m, 4H, 2ꢁCH ). C NMR (CDCl3)
2
2
d: 170.3, 135.2, 133.0, 130.4, 127.5, 126.2, 125.2, 66.4,
66.3, 48.0, 42.0. IR (KBr, cm ): 1632 (CON). MS m/z
(rel int. %): 354 (3), 268 (100), 224 (16), 180 (37), 127
ꢀ
ꢂ1
(24). Anal. Calcd for C H N O (354.41): C, 67.78; H,
6.26; N, 7.90. Found: C, 67.59; H, 6.45; N, 7.76. R (10%
EtOAc/CHCl ) 0.18; off-white solid, mp 77 C.
3
20 22 2 4
4
1
.4. Aminocarbonylation experiments towards
,8-naphthalimides at high pressure
f
ꢀ
0 0 0
4.5.4. 1-[N,N-(3 -Oxa-penta-1 ,5 -diyl)-carboxamido]-8-
In a typical experiment a solution of Pd(OAc) (5.6 mg,
2
00 00 00
[N,N-(3 -oxa-penta-1 ,5 -diyl)-glyoxylamido]-naphtha-
lene (2 e). H NMR (CDCl ) d: 8.08 (m, 2H, Naph), 7.95 (d,
0
.025 mmol), PPh (13.1 mg, 0.05 mmol), 1,8-diiodo-naph-
3
0
1
thalene (1, 0.5 mmol), unfunctionalised primary amine (a–c,
.55 mmol) (or amino acid methylester hydrochlorides pos-
sessing primary amine functionality (f–h)) and triethylamine
1.0 ml) was dissolved in 10 ml DMF under argon into
3
0
8.0 Hz, 1H, Naph), 7.52–7.58 (m, 3H, Naph), 3.55–3.95 (m,
16H, 8ꢁCH ). C NMR (CDCl ) d: 192.9, 171.1, 165.2,
1
3
2
3
(
135.9, 135.4, 133.6, 133.3, 130.9, 130.6, 130.4, 128.8,
126.2, 125.2, 67.0, 66.6, 66.3, 66.0, 48.7, 45.9, 42.1, 42.0.
a 100 ml stainless steel autoclave. The reaction vessel was
pressurised to 40 bar total pressure with carbon monoxide
and the magnetically stirred mixture was heated in an oil
ꢂ1
IR (KBr, cm ): 1673 (CO), 1643 (br, 2ꢁCON). MS m/z
(rel int. %): 382 (3), 297 (6), 268 (100), 224 (11), 180
(30), 126 (13). Anal. Calcd for C H N O (382.42): C,
ꢀ
bath at 50 C for up to 90 h.
2
1 22 2 5
6
R (50% EtOAc/CHCl ) 0.27; off-white solid, mp 77 C.
5.96; H, 5.80; N, 7.33. Found: C, 65.79; H, 5.85; N, 7.16.
ꢀ
Some metallic palladium was formed at the end of the re-
action, which was filtered. (A sample of this solution was
immediately analysed by GC–MS.) The mixture was then
concentrated and evaporated to dryness. The residue was
dissolved in chloroform (20 ml) and washed with water
f
3
4.5.5. N-(tert-Butyl)-1,8-naphthalimide (3a). MS m/z (rel
int. %): 253 (5), 238 (100), 180 (73), 153 (30), 126 (25).
1
4
1
(
with 5% HCl (20 ml), saturated NaHCO (20 ml), brine
20 ml). The organic phase was thoroughly washed twice
4.5.6. N-Phenyl-1,8-naphthalimide (3b). H NMR
(CDCl ) d: 8.64 (d, 7.6 Hz, 2H, Naph), 8.26 (d, 8.2 Hz, 2H,
Naph), 7.92 (t, 7.6, 8.2 Hz, 2H, Naph), 7.55 (t, 7.2 Hz, 2H,
3
3
(
20 ml), dried over Na SO and concentrated to a yellow
4
2
1
3
waxy material. Chromatography (silica, EtOAc/CHCl ¼
Ph), 7.47 (t, 7.2 Hz, 1H, Ph), 7.32 (d, 7.2 Hz, 2H, Ph).
NMR (CDCl ) d: 164.3, 135.2, 134.2, 133.3, 129.3, 128.6,
C
3
1
thalimides (3b, 3c, 3f–3h) as solids.
/9, then chloroform/ethanol¼1/1) yielded the desired naph-
3
ꢂ1
128.5, 127.4, 126.9, 122.8. IR (KBr, cm ): 1662 (CON).
MS m/z (rel int. %): 273 (81), 272 (100), 228 (38), 180
4
4
.5. Characterization of the products
(30), 126 (26). Anal. Calcd for C H NO (273.29): C,
1
8
11
2
79.11; H, 4.06; N, 5.13. Found: C, 79.02; H, 4.25; N, 5.02.
R (10% EtOAc/CHCl ) 0.76; yellow solid, mp 182 C. The
0
0
ꢀ
spectral data were in accordance with the literature data.
.5.1. 1,8-Bis(N,N-penta-1 ,5 -diyl-carboxamido)-naph-
f
3
1
thalene (2d). H NMR (CDCl ) d: 7.82 (d, 8.1 Hz, 2H,
3
Naph), 7.42 (t, 7.0, 8.1 Hz, 2H, Naph), 7.36 (d, 7.0 Hz,
2
1
5
1
H, Naph), 4.12 (d, 2H, 12 Hz, 2N(CH H )), 3.18–3.40
b
4.5.7. N-Benzyl-1,8-naphthalimide (3c). H NMR
(CDCl ) d: 8.59 (d, 7.6 Hz, 2H, Naph), 8.18 (d, 8.2 Hz, 2H,
a
(
m, 6H, (CH ) +2N(CH H )), 1.4–1.8 (m, 12H, 2ꢁ(CH ) ).
2
2
a
b
2 3
3
1
3
C NMR (CDCl ) d: 169.7, 134.9, 134.4, 129.7, 126.9,
3
Naph), 7.72 (t, 7.6, 8.2 Hz, 2H, Naph), 7.52 (d, 7.2 Hz, 2H,
Ph), 7.20–7.31 (m, 3H, Ph), 5.39 (s, 2H, CH2). C NMR
ꢂ1
13
1
25.7, 125.2, 48.4, 42.2, 25.7, 25.3, 24.6. IR (KBr, cm ):
1
625 (CON). MS m/z (rel int. %): 350 (9), 265 (80), 238
36), 180 (42), 127 (28), 84 (100). Anal. Calcd for
(CDCl ) d: 164.1, 137.3, 133.9, 131.5, 131.3, 128.9, 128.4,
3
127.4, 126.9, 122.6, 43.5. IR (KBr, cm ): 1655 (CON).
MS m/z (rel int. %): 287 (100), 207 (14), 181 (46), 153
ꢂ1
(
C H N O (350.46): C, 75.40; H, 7.48; N, 7.99. Found:
2
2 26 2 2
C, 75.20; H, 7.65; N, 7.72. R (10% EtOAc/CHCl ) 0.48;
f
off-white solid, mp 190 C.
(56), 127 (34). Anal. Calcd for C H NO (287.32): C,
19 13
79.43; H, 4.56; N, 4.87. Found: C, 79.32; H, 4.72; N, 4.67.
3
2
ꢀ

A. Tak aꢀ cs et al. / Tetrahedron 64 (2008) 983–987
987
ꢀ
spectral data were in accordance with the literature data.
R (10% EtOAc/CHCl ) 0.84; off-white solid, mp 192 C. The
f
References and notes
3
1
. Applied Homogeneous Catalysis with Organometallic Com-
pounds; Cornils, B., Herrmann, W. A., Eds.; Wiley-VCH:
Weinheim, 1996.
4
(
.5.8. N-(Methoxycarbonyl-methyl)-1,8-naphthalimide
3f). H NMR (CDCl ) d: 8.58 (d, 7.6 Hz, 2H, Naph), 8.20
1
3
(
d, 8.2 Hz, 2H, Naph), 7.72 (t, 7.6, 8.2 Hz, 2H, Naph),
.95 (s, 2H, CH ), 3.76 (s, 3H, OCH ). C NMR (CDCl3)
2 3
2. Transition Metals for Organic Synthesis; Beller, M., Bolm, C.,
Eds.; Wiley-VCH: Weinheim, 1998; Vols. I–II.
3. Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V.
Carbonylation: Direct Synthesis of Carbonyl Compounds;
Plenum: New York, NY and London, 1991.
1
3
4
d: 168.5, 163.8, 135.2, 134.3, 133.3, 127.4, 126.9, 122.1,
5
MS m/z (rel int. %): 269 (31), 237 (21), 210 (100), 180
ꢂ1
2.4, 41.2. IR (KBr, cm ): 1753 (COO), 1661 (CON).
(
30), 126 (24). Anal. Calcd for C H NO (269.26): C,
4
4. Skoda-F €o ldes, R.; Koll ꢀa r, L. Curr. Org. Chem. 2002, 6, 1097–
1119.
5. M €u ller, E.; P ꢀe czely, G.; Skoda-F €o ldes, R.; Tak ꢀa cs, E.; Kokotos,
G.; Bellis, E.; Koll ꢀa r, L. Tetrahedron 2005, 61, 797–802.
6. Freskos, J. N.; Ripin, D. H.; Reilly, M. L. Tetrahedron Lett.
1993, 34, 255–256.
1
5
11
6
R (10% EtOAc/CHCl ) 0.67; white solid, mp 167 C.
6.91; H, 4.12; N, 5.20. Found: C, 66.70; H, 4.25; N, 5.01.
ꢀ
f
3
0
.5.9. N-(1 -Methoxycarbonyl-ethyl)-1,8-naphthalimide
3g). H NMR (CDCl ) d: 8.58 (d, 7.6 Hz, 2H, Naph), 8.20
4
(
1
3
(
d, 8.2 Hz, 2H, Naph), 7.72 (t, 7.6, 8.2 Hz, 2H, Naph),
7. Hua, D. H.; McGill, J. W.; Lou, K.; Ueki, A.; Helfrich, B.;
Desper, J.; Zanello, P.; Cinquantini, A.; Corsini, M.; Fontani, M.
Inorg Chim. Acta 2003, 350, 259–265.
8. Sato, M.; Maruyama, G.; Tanemura, A. J. Organomet. Chem.
2002, 655, 23–30.
5
7
1
.75 (q, 7 Hz, 1H, CHCH ), 3.70 (s, 3H, OCH ), 1.67 (d,
3 3
1
3
Hz, 3H, CH3). C NMR (CDCl ) d: 170.9, 163.5, 135.3,
3
34.2, 133.3, 127.4, 126.9, 122.4, 52.3, 49.0, 14.7. IR
ꢂ1
(
KBr, cm ): 1738 (COO), 1660 (CON). MS m/z (rel int.
%
): 283 (34), 251 (21), 224 (100), 180 (46), 126 (27).
Anal. Calcd for C H NO (283.28): C, 67.84; H, 4.63;
9. Chang, S. C.; Utecht, R. E.; Lewis, D. E. Dyes Pigments 1999,
43, 83–94.
1
6
13
4
N, 4.94. Found: C, 67.61; H, 4.75; N, 4.76. R (10%
f
EtOAc/CHCl ) 0.70; yellow solid, mp 143 C.
3
10. Bojinov, V.; Ivanova, G.; Chovelon, J. M.; Grabchev, I. Dyes
Pigments 2003, 58, 65–71.
ꢀ
1
1. Jia, L. H.; Zhang, Y.; Guo, X. F.; Qian, X. H. Tetrahedron Lett.
2004, 45, 3969–3973.
0 0
.5.10. N-(1 -Methoxycarbonyl-2 -methyl-propyl)-1,8-
naphthalimide (3h). H NMR (CDCl ) d: 8.60 (d, 7.6 Hz,
4
1
3
12. Yang, J. X.; Wang, X. L.; TusongXu, L. H. Dyes Pigments
2005, 67, 27–33.
13. Nagao, Y.; Iwawaki, H.; Kozawa, K. Heterocycles 2002, 56,
331–340.
14. Barooah, N.; Tamuly, C.; Baruah, J. B. J. Chem. Sci. 2005, 117,
117–122.
15. Cao, H.; Chang, V.; Hernandez, R.; Heagy, M. D. J. Org. Chem.
2005, 70, 4929–4934.
16. Chernick, E. T.; Ahrens, M. J.; Scheidt, K. A.; Wasiliewski,
M. R. J. Org. Chem. 2005, 70, 1486–1489.
17. Day, J. C.; Govindaraj, N.; McBain, D. S.; Skell, P. S.; Tanko,
J. M. J. Org. Chem. 1986, 51, 4959–4963.
2
8
3
7
H, Naph), 8.22 (d, 8.2 Hz, 2H, Naph), 7.78 (t, 7.6,
.2 Hz, 2H, Naph), 5.37 (d, 7.4 Hz, 1H, NCH), 3.66 (s,
H, OCH ), 2.80–2.88 (m, 1H, CH(CH ) ), 1.31 (d,
3
3 2
1
3
.1 Hz, 3H, CHCH ), 0.8 (d, 7.1 Hz, 3H, CHCH ).
3
C
3
NMR (CDCl ) d: 170.3, 163.9, 135.2, 134.2, 133.4, 126.9,
3
ꢂ1
1
(
(
22.2, 58.4, 52.0, 27.6, 22.0, 19.0. IR (KBr, cm ): 1736
COO), 1663 (CON). MS m/z (rel int. %): 311 (40), 237
18), 198 (100), 180 (52), 126 (28). Anal. Calcd for
C H NO (311.34): C, 69.44; H, 5.50; N, 4.50. Found:
17
1
8
4
C, 69.22; H, 5.57; N, 4.38. R (10% EtOAc/CHCl ) 0.77;
f
3
ꢀ
pale yellow solid, mp 158 C.
1
8. Zheng, S.; Lan, J.; Khan, S. I.; Rubin, Y. J. Am. Chem. Soc.
2003, 125, 5786–5791.
9. House, H. O.; Koepsell, D. G.; Campbell, W. J. J. Org. Chem.
Acknowledgements
1
The authors thank the Hungarian Research Fund (OTKA
NI61591) and the Joint Project of the European Union—
Hungarian National Development Program (GVOP-3.2.1-
1972, 37, 1003–1011.
20. Tak ꢀa cs, E.; Skoda-F €o ldes, R.; Acs, P.; M €u ller, E.; Kokotos, G.;
Koll ꢀa r, L. Lett. Org. Chem. 2006, 3, 62–67.
ꢀ
2004-04-0168/3) for the financial support and Johnson
Matthey for the generous gift of palladium(II) acetate.
21. Skoda-F €o ldes, R.; Cs ꢀa kai, Z.; Koll ꢀa r, L.; Szalontai, G.;
Horv ꢀa th, J.; Tuba, Z. Steroids 1995, 60, 786–790.