Malamidou-Xenikaki et al.
SCHEME 8
1H), 9.51 (s, br, 1H), 7.65-7.49 (m, 6H), 7.38 (t, J ) 7 Hz,
2
1
1
H), 7.20 (t, J ) 7 Hz, 1H); 13C NMR (CDCl
, 75 MHz) δ 192.7,
3
90.3, 165.2, 137.5, 137.3, 135.6, 133.4, 133.1, 129.3, 125.6,
21.9, 121.5, 121.0, 96.0; MS m/z 265 (M , 91), 173 (84), 146
+
(
19), 93 (100). Anal. Calcd for C16
N, 5.28. Found: C, 72.21; H, 4.21; N, 5.38.
,3-Dioxo-N-(p-tolyl)-2-in d a n ca r boxa m id e (5b): yield
3
H11NO : C, 72.45; H, 4.18;
1
1
9
4%; mp 167-170 °C; H NMR (CDCl
br, 1H), 9.52 (s, br, 1H), 7.70-7.54 (m, 4H), 7.40 (d, J ) 8 Hz,
H), 7.19 (d, J ) 8 Hz, 2H), 2.36 (s, 3H); 13C NMR (CDCl
, 75
MHz) δ 193.2, 190.4, 165.2, 137.7, 135.7, 133.4, 133.0, 132.9,
3
, 300 MHz) δ 10.80 (s,
2
3
+
1
29.9, 121.9, 121.5, 121.2, 95.6, 21.0; MS m/z 279 (M , 87),
73 (76), 146 (14), 107 (95), 106 (100). Anal. Calcd for C17
: C, 73.11; H, 4.69; N, 5.02. Found: C, 73.03; H, 4.51; N,
4.89.
,3-Dioxo-N -(p -m e t h oxyp h e n yl)-2-in d a n ca r b oxa m -
1
NO
13
H -
3
SCHEME 9
1
1
3
id e (5c): yield 75%; mp 140-143 °C; H NMR (CDCl , 300
MHz) δ 9.50 (s, br, 1H), 7.84 (s, br, 1H), 7.68-7.53 (two
overlapping m, 4H), 7.42 (d, J ) 9 Hz, 2H), 6.91 (d, J ) 9 Hz,
2
1
1
H), 3.82 (s, 3H); 13C NMR (CDCl
65.0, 157.6, 137.8, 133.4, 133.0, 128.3, 123.0, 121.9, 121.4,
16.6, 114.5, 95.4, 55.5; MS m/z 295 (M , 44), 173 (53), 146
, 75 MHz) δ 193.2, 190.4,
3
+
sone (12) was prepared. The copper-catalyzed reaction
of 12 with aniline afforded N-phenyl-p-tolylamine (4b),
(
18), 123 (85). Labile compound. No satisfactory elemental
analysis could be obtained.
8
, and the corresponding p-tolyl ether 13, thus verifying
1,3-Dioxo-N-(p-n itr op h en yl)-2-in d a n ca r boxa m id e (5d ):
1
that both amination and aryl migration take place at the
carbon ipso to iodine (Scheme 8).
Finally, in one case, namely the reaction of 3 with
â-phenylethylamine (4g), a red solid was crystallized out
from the reaction mixture. On the basis of spectroscopic
and analytical data, this solid proved to be imine 14 in
yield 89%; mp 248-250 °C; H NMR (CDCl
3
, 300 MHz) δ 9.61
(s, br, 1H), 8.27 (d, J ) 8 Hz, 2H), 7.79 (d, J ) 8 Hz, 2H),
7
1
.65-7.57 (m, 5H); 13C NMR (CDCl
93.9, 190.0, 162.8, 158.9, 96.4. Due to solubility reasons, the
3
+ DMSO-d , 75 MHz) δ
6
solution was heated in order to dissolve and partially decom-
posed to give two many peaks in the aromatic region: MS m/z
+
3
10 (M , 61), 173 (82), 146 (8), 138 (100). Anal. Calcd for
1
8% yield. On passing 14 through a silica gel column, it
16 10 2 5
C H N O : C, 61.94; H, 3.25; N, 9.03. Found: C, 61.56; H,
was hydrolyzed to hydroxyiodoquinone 8 and initial
amine 4g (Scheme 9). This finding indicates that also in
other reactions with amines analogous imines may have
been formed but not detected. This assumption also
explains the fact that, although the amine is consumed
toward the end of the reaction (checked by TLC in the
reaction mixture), yields of arylated amines are not very
high.
3.55; N, 8.93.
1,3-Dioxo-N-(o-tolyl)-2-in d a n ca r boxa m id e (5e): yield
97%; mp 163-165 °C; H NMR (CDCl
br, 1H), 8.17 (s, br, 1H), 7.82 (d, J ) 7 Hz, 1H), 7.65-7.52 (m,
1
3
, 300 MHz) δ 9.63 (s,
4
H), 7.31-7.21 (m, 2H), 7.15 (t, J ) 7 Hz, 1H), 2.43 (s, 3H);
1
3
C NMR (CDCl , 75 MHz) δ 193.1, 190.6, 165.4, 137.7, 133.8,
3
1
9
33.5, 133.1, 130.9, 129.5, 126.9, 126.1, 122.7, 121.9, 121.6,
5.9, 17.8; MS m/z 279 (M , 100), 173 (90), 146 (16), 107 (87).
+
Anal. Calcd for C17
C, 73.33; H, 4.56; N, 4.71.
1,3-Dioxo-N-ben zyl-2-in d a n ca r boxa m id e (5f): yield 73%;
3
H13NO : C, 73.11; H, 4.69; N, 5.02. Found:
In conclusion, the reaction of iodonium ylides of hy-
droxyquinones with amines follows two different reaction
pathways: Under thermal conditions (or Pd catalysis),
good yields of indanedione carboxamides are isolated
through the intermediacy of highly active R,R′-diox-
oketene. These carboxamides exist in the interesting
enol-amide structure. In the Cu2 -catalyzed correspond-
ing reactions, arylation of the amine takes place in
moderate yields. Iodoquinone 8, bearing a most unusual
for hydroxyquinones o-quinonic structure, is also isolated
from the same reactions.
1
mp 150-152 °C; H NMR (CDCl
3
, 300 MHz) δ 10.24 (s, br,
1
7
7
1
1
7
H), 8.19 (s, br, 1H), 7.63-7.58 (m, 2H), 7.54-7.49 (m, 2H),
.41-7.29 (m, 5H), 4.63 (s, 1H), 4.61 (s, 1H); 13C NMR (CDCl
,
3
5 MHz) δ 193.3, 190.2, 167.1, 138.1, 136.2, 133.0, 131.9, 128.9,
28.1, 127.6, 121.4, 94.4, 43.5; MS m/z 279 (M , 57), 173 (25),
46 (43), 107 (69), 106 (100). Anal. Calcd for C17H13NO : C,
3
3.11; H, 4.69; N, 5.02. Found: C, 72.95; H, 4.45; N, 5.05.
+
+
1,3-Dioxo-N-(2′-p h en yleth yl)-2-in d a n ca r boxa m id e (5g):
yield 88%; mp 165-167 °C; H NMR (CDCl
1
3
, 300 MHz) δ 10.67
(s, br, 1H), 7.93 (s, br, 1H), 7.64-7.57 (m, 2H), 7.55-7.48 (m,
H), 7.37-7.18 (m, 5H), 3.70 and 3.68 (two t overimposed, J
) 7 Hz, 2H), 2.94 (t, J ) 7 Hz, 2H); 13C NMR (CDCl
, 75
MHz) δ 193.3, 190.2, 167.1, 138.3, 137.5, 132.9, 128.9, 128.7,
2
1
)
J
2
3
Exp er im en ta l Section
+
1
1
27.0, 121.3, 93.9, 41.1, 35.7; MS m/z 293 (M , 70), 173 (100),
46 (33), 121 (11), 120 (43). Anal. Calcd for C18 : C,
Gen er a l P r oced u r e for th e Th er m a l Rea ction of 3 w ith
H
15NO
3
Am in es. A suspension of 2-oxido-3-phenyliodonio-1,4-naph-
3
73.71; H, 5.15; N, 4.78. Found: C, 73.92; H, 4.91; N, 4.45.
1,3-Dioxo-N-[(p h en yl)(m et h yl)]-2-in d a n ca r b oxa m id e
thoquinone (3) (1 mmol) and the corresponding amine 4 (1
mmol) in CH
solution resulted and TLC showed the disappearance of ylide
. The solution was concentrated in a vacuum to half its
2
Cl
2
(15 mL) was refluxed for 4-7 h until a clear
1
(5h ): yield 79%; mp 127-130 °C; H NMR (CDCl
3
, 300 MHz)
3
δ 13.87 (s, br, 0.4H, enolic form), 8.01-7.92 (m, 2H), 7.85-
7.78 (m, 2H), 7.60-7.25 (m, aromatic H for both forms), 4.21
volume, hexanes (∼10 mL) was added, and the precipitated
yellow solid was filtered and washed repeatedly with hexanes.
An analytical sample was obtained by recrystallization from
1
3
(s, 1H), 3.64(s, 1.2H, Me for the enolic form), 3.37 (s, 3H);
NMR (CDCl
C
3
, 75 MHz) δ characteristic peaks 194.5, 168.1,
+
CH
2
Cl
2
-hexanes. For simplicity reasons, compounds 5 are
164.7, 95.8, 58.8, 40.6, 37.5 (both forms); MS m/z 279 (M , 58),
173 (31), 146 (56), 108 (100), 107 (53). Labile compound. No
satisfactory elemental analysis could be obtained.
named according to their amide tautomeric form (e.g., com-
pound 5a in its enol-amide form should be named 2-[anilino-
(hydroxy)methylidene]-1H-indene-1,3(2H)-dione).
Gen er a l P r oced u r e for th e Cu -Ca ta lyzed Rea ction of
3 w ith Am in es. A suspension of 2-oxido-3-phenyliodonio-1,4-
naphthoquinone (3) (1 mmol), the corresponding amine 4 (1
1
,3-Dioxo-N-ph en yl-2-in dan car boxam ide (5a): yield 84%;
1
mp 144-146 °C; H NMR (CDCl
3
, 300 MHz) δ 11.87 (s, br,
5
630 J . Org. Chem., Vol. 68, No. 14, 2003