Reaction of 2,5-dimethylpyrroles with quinones. Synthesis of new pyrrolylquinones dyes

Article abstract of DOI:10.1002/jhet.5570390118

The reaction of 1,4-naphthoquinone (1) with 2,5-dimethylpyrroles (7a-7d) gives only 3-(1,4-naphthoquinonyl)-2,5-dimethylpyrroles. Extending the reaction to other quinones: 5-hydroxy-1,4-naphthoquinone (2), 1,2-naphthoquinone (3), quinoline-5,8-dione (4) and quinoxaline-5,8-dione (5), of which nothing was known, allows the synthesis of new pyrrolylquinones.

Full text of DOI:10.1002/jhet.5570390118

Jan-Feb 2002
Reaction of 2,5-Dimethylpyrroles with Quinones.
Synthesis of New Pyrrolylquinones Dyes
125
Claude Lion*, Richard Baudry, Mir Hedayatullah and Louis Da Conceição
Institut de Topologie et de Dynamique des Systèmes, Université Paris 7 - Denis Diderot, associé au CNRS,
1
rue Guy de la Brosse, 75005 Paris, France
Sylvie Genard and Jean Maignan
Centre de Recherche Avancée de l’OREAL, 1 avenue Eugène Schueller, 93601 Aulnay-sous-Bois, France
Received May 30, 2000
The reaction of 1,4-naphthoquinone (1) with 2,5-dimethylpyrroles (7a-7d) gives only 3-(1,4-naphtho-
quinonyl)-2,5-dimethylpyrroles. Extending the reaction to other quinones: 5-hydroxy-1,4-naphthoquinone
2), 1,2-naphthoquinone (3), quinoline-5,8-dione (4) and quinoxaline-5,8-dione (5), of which nothing was
known, allows the synthesis of new pyrrolylquinones.
(
J. Heterocyclic Chem., 39, 125 (2002).
Introduction.
The general pathway for the synthesis of monoquinonyl-
or diquinonylpyrroles is given in Scheme 2 [1-3]:
Usually the reaction gives a complex mixture of mono-
and di-quinonylpyrroles besides polymers and tars. It is
known that the 2 and 5 positions of the pyrroles are the
most reactive and give polymers in the presence of metal-
lic salts [1a]. In all cases the pyrroles (6) used had free 2
and 5 positions.
In a previous paper [1a] we reported the synthesis of
new organic dyes in the pyrrolylnaphthoquinone family.
The structures were obtained by the reaction of 1,4-naph-
thoquinone (1), 5-hydroxy-1,4-naphthoquinone (juglone,
2
), 1,2-naphthoquinone (3), quinoline-5,8-dione (4) and
quinoxaline-5,8-dione (5) with N-alkylated pyrroles (6)
1,2], (Scheme 1).
[
Scheme 1
Scheme 2

1
26
C. Lion, R. Baudry, M. Hedayatullah, L. Da Conceição, S. Genard and J. Maignan
b- Quinoxaline-5,8-dione (5).
Vol. 39
Our interest in the preparation of new dyes for hair col-
oration [1b] prompted us to use 2,5-disubstituted pyrroles
to avoid secondary products. Very little is known about the
reactions of 2,5-disubstituted pyrroles with naphtho-
quinones. Some previous papers [4-6] reported the reac-
tion of 1,4-benzoquinones with 2,5-dimethylpyrrole lead-
ing to disubstituted 3,4-dibenzoquinonyl-2,5-dimethyl-
pyrroles or the substitution reaction of 2,3-dichloronaph-
thoquinone with 1,2,5-trimethylpyrrole giving 2-chloro-3-
Compound (5) is obtained in five steps from commercial
,4-dimethoxybenzene. The nitration of this product leads
1
to a mixture of 2,5-dinitro- (64%) and 2,3-dinitro-1,4-
dimethoxybenzene (16%) [9]. The two isomers are used
without separation [10]; catalytic hydrogenation [11] fol-
lowed by condensation with glyoxal gives pure 5,8-
dimethoxyquinoxaline and allows the separation from 2,3-
dinitro-1,4-dimethoxybenzene. The hydrogenation step
was also performed with tin in HCl [12]. Different methods
for demethylation of the dimethoxyquinoline [11,13-15]
give quinoxaline-5,8-dione (5); best results were obtained
by using ceric ammonium nitrate (CAN) [14]. The overall
yield of the synthesis is about 13% (Scheme 5).
[
3-(1,2,5-trimethylpyrrolyl)]-1,4-naphthoquinone [7].
We describe here our results on the reaction of quinones
1-5) with 2,5-disubstituted pyrroles (7) (Scheme 3): new
(
organic dyes have been synthesized by this method and
tested for application in hair coloration [1b].
Scheme 3
II- Condensation of Pyrroles (7a-7d) with Quinones.
a- 1,4-Naphthoquinone (1) and 5-Hydroxy-1,4-naphtho-
quinone (2).
The best yield is observed using acetic acid, with an
excess of naphthoquinone to oxidise the intermediate
hydroquinone at room temperature. The reaction is com-
plete in two hours and gives compounds (8a-8d) besides
polymers and tars.
Results-Discussion.
I- Quinone Synthesis.
a- Quinoline-5,8-dione (4).
In the case of 5-hydroxy-1,4-naphthoquinone (2) under
the same conditions, the yields are lower than with 1,4-
naphthoquinone (1), and the only compound (9a-9d)
obtained has the pyrrole substituent at the 3 position of
juglone (2). The structures were assigned by nmr studies of
This compound is prepared in three steps from commer-
cial 8-hydroxyquinoline. The nitrosation of 8-hydrox-
yquinoline followed by reduction leads to 5-amino-8-
hydroxyquinoline which by hydrolysis and oxidation
affords quinone (4) in 29% overall yield [8] (Scheme 4).
1
3
1
long-distance heteronuclear C− H coupling [15]. The
1
3
nmr C spectrum of (9c) (Figure) shows the C and C
1
4
Scheme 4
Reagents: i, NaNO , HCl; ii, 5N NaOH; iii, Na S O ; iv, 12N H SO ; v, K Cr O , 12N H SO .
2
2
2
4
2
4
2
2
7
2
4
Scheme 5
Reagents: i, HNO , AcOH; ii, H (2-3 bars), PtO , EtOH; iii, [CH(OH)SO Na] , H O; iv, Ce(NH ) (NO ) , CH CN.
3
2
2
3
2
2
4 2
3 6
3

Jan-Feb 2002
Reaction of 2,5-Dimethylpyrroles with Quinones
127
atoms as a singlet (δ: 184.5 ppm) and a doublet (δ: 191.2
ppm, JC4-H2= 10.2 Hz), respectively, in accordance of the
literature values for pyrrole substitution at the 3 position of
juglone [16].
c- Quinoline-5,8-dione (4) and Quinoxaline-5,8-dione (5).
3
The reaction is performed in a water/chloroform mixture
(1:1) with 20% of acetic acid using an excess of pyrrole
and FeCl as complexing and oxidising agent [2,18].
3
Under these conditions only compounds with the pyrrolyl
at the 6 position of the quinoline-5,8-dione (4) are
obtained. The reaction is rapid but in the case of 2,5-
dimethylpyrrole (7a) the condensation product (12a) is not
Scheme 6
isolated; a metallic salt such as FeCl is well known to
3
polymerise 2,5-dimethylpyrrole [19] (Table).
Scheme 8
Neither with 1,4-naphthoquinone (1) nor with
5
-hydroxy-1,4-naphthoquinone (2) were disubstituted
quinonylpyrroles obtained [1].
1
94
193
192
191
190
189
188
PPM
187
186
185
184
183
Figure
b- 1,2-Naphthoquinone (3).
The structures (12a-12d) were assigned by comparison
of the nmr data with literature values [20]. It has also been
In acetic acid the reaction of (3) with pyrroles (7) is fast
and gives polymers and tars. In ethyl alcohol with a cat-
alytic amount of p-toluenesulfonic acid at room tempera-
ture the reaction is slow and leads to 60-70% of the
quinonylpyrroles (10, 11) (Table).
shown that in the presence of FeCl •6H O (Scheme 8)
3
2
only the 6-substituted isomers are formed [20].
Scheme 9
Scheme 7

128
C. Lion, R. Baudry, M. Hedayatullah, L. Da Conceição, S. Genard and J. Maignan
Vol. 39
In the case of 5,8-quinoxalinedione, the condensation is
very slow and 44-61% of product (13b-13d) is formed
General Procedure for the Preparation of Compounds (8a-8d)
and (9a-9d).
after 48 hours reaction.
A solution of 1,4-naphthoquinone (1) or 5-hydroxy-1,4-naph-
thoquinone (2) (40 mmol) and pyrrole (7, 10 mmol) in glacial
acetic acid (50 mL) was stirred for two hours at room tempera-
ture. The solvent was removed under vacuum and the residue dis-
solved in chloroform (50 mL) and water (50 mL). Extraction by
chloroform (3 X 100 mL), washing the combined organic solu-
tions with a saturated solution of sodium carbonate (30 mL), then
Table
Entry
Quinone
Pyrrole
Compound Yield (%) Mp (°C)
1
2
3
4
5
6
7
8
9
1
7a
7b
7c
7d
7a
7b
7c
7d
7b
7d
7a
7b
7c
7d
7a
7b
7c
7d
8a
8b
8c
8d
9a
9b
9c
9d
56
39
42
51
37
31
33
26
72
65
0 [a]
19
59
22
0 [a]
44
56
177-179
209-210
162-163
184-186
195-196
182-183
181-182
172-174
176-179
188-189
-
220-221
237-241
171-172
-
209-210
196-197
235-237
with water (50 mL) gave after drying (MgSO ) the crude prod-
4
ucts. The pyrrolylquinones (8a-8d and 9a-9d) were isolated by
column chromatography [SiO , CHCl ].
2
2
3
2-(2,5-Dimethyl-1H-pyrrol-3-yl)-1,4-naphthoquinone (8a).
This compound was obtained as a red solid (56%), mp 177-179
3
4
10
11
1
°
C; H nmr (CDCl ): δ 2.28 (s, 3H), 2.39 (s, 3H), 6.24 (dq, 1H,
3
1
0
J = 0.9 Hz, J = 2.9 Hz), 6.84 (s, 1H), 7.68-7.77 (m, 2H), 7.93 (s,
1
1
12a
12b
12c
12d
13a
13b
13c
13d
+
1
H), 8.08-8.17 (m, 2H); ms (isobutane) m/z 252 (MH ); uv
1
1
1
1
1
1
1
2
3
4
5
6
7
8
(
3
THF) λ
(lg ε) = 248 (4.13), 294 (4.05), 501 (3.40); ir (KBr) ν
max
290 cm-1 (N-H), 1640, 1665 cm (C=O); hrms (FAB) m/z
-1
+
Calcd. for C H NO (MH ): 252.1025; Found: 252.1024.
5
16 14
2
Methyl 4-(1,4-Dioxo-1,4-dihydronaphthalen-2-yl)-2,5-dimethyl-
1
H-pyrrole-3-carboxylate (8b).
61
This compound was obtained as a orange solid (39%), mp 209-
[
a] Tars, polymers.
1
2
3
1
(
(
10 °C; H nmr (CDCl ): δ 2.20 (s, 3H), 2.46 (s, 3H), 3.61 (s,
3
H), 6.77 (s, 1H), 7.70-7.78 (m, 2H), 8.06-8.16 (m, 2H), 8.57 (s,
+
H); ms (isobutane) m/z 309 (M ); uv (THF) λ
(lg ε) = 294
max
In this work we have prepared new 2,5-dimethyl-
-1
3.68), 245 (4.01), 266 (3.92), 453 (3.10); ir (KBr) ν 3360 cm
N-H), 1640, 1665 cm (C=O, quinone), 1710 cm (C=O,
ester); hrms (FAB) m/z Calcd. for C H NO (MH+): 310.1079;
pyrrolylquinones from several quinones (1-5). When the
reactive 2 and 5 positions of the pyrrole are substituted, the
reaction with quinones occurs in the 3 position. New 2,5-
dimethylpyrrolylquinones in the 1,4-naphthoquinone, 1,2-
naphthoquinone, quinoline-5,8-dione and quinoxaline-5,8-
dione series have been obtained.
-1
-1
1
8
16
4
Found: 310.1073.
2
-(1,2,5-Trimethyl-1H-pyrrol-3-yl)-1,4-naphthoquinone (8c).
This compound was obtained as a red solid (42%), mp 162-163
1
°
C; H nmr (CDCl ): δ 2.26 (s, 3H), 2.32 (s, 3H), 3.45 (s, 3H), 6.20
3
(
(
(
s, 1H), 6.80 (s, 1H), 7.70-7.75 (m, 2H), 8.07-8.17 (m, 2H); ms
+
isobutane) m/z 266 (MH ); uv (THF) λ
(lg ε) = 248 (4.15), 295
EXPERIMENTAL
max
-1
4.04), 502 (3.53); ir (KBr) ν 1640, 1670 cm (C=O); hrms (FAB)
+
m/z Calcd. for C H NO (MH ): 266.1181; Found: 266.1177.
17
16
2
With the exception of quinones (4) and (5), all starting materials
1, 2, 3, 7a-7d) were purchased from Aldrich. Melting points were
(
Methyl 4-(1,4-dioxo-1,4-dihydronaphthalen-2-yl)-1,2,5-
trimethyl-1H-pyrrole-3-carboxylate (8d).
taken on a Mettler FP 5 capillary apparatus. The ir spectra were
recorded on a Perkin-Elmer 781 spectrophotometer. The uv spectra
were recorded on a Shimadzu UV/Vis 240 spectrophotometer. The
H and C nmr spectra were run on a Bruker W 200 spectropho-
tometer at 200 MHz and 50 MHz, respectively, using CDCl or
DMSO-d as the solvent and are referenced to tetramethylsilane
TMS). The mass spectra were obtained on a Finnigan Mat 800
ITD coupled with a CP - Sil 5 GC column (chemical ionisation
using isobutane) or a Nermag R-30-10 (with direct introduction,
This compound was obtained as a orange solid (51%), mp 184-
1
1
3
86 °C; H nmr (CDCl ): δ 2.22 (s, 3H), 2.53 (s, 3H), 3.47 (s, 3H),
3
1
13
.57 (s, 3H), 6.70 (s, 1H), 7.71-7.78 (m, 2H), 8.08-8.15 (m, 2H);
+
3
ms (isobutane) m/z 323 (M ); uv (THF) λ
263 (3.96), 294 (3.64), 322 (3.46), 452 (3.14); ir (KBr) ν 1660,
1
(lg ε) = 244 (4.08),
max
6
(
-1
-1
670 cm (C=O, quinone), 1710 cm (C=O, ester); hrms (FAB)
+
m/z Calcd. for C H NO (MH ): 324.1236; Found: 324.1234.
19
18
4
2
-(2,5-Dimethyl-1H-pyrrol-3-yl)-5-hydroxy-1,4-naphthoquinone
chemical ionisation using NH ). All the compounds have one spot
3
(9a).
by tlc on silica gel 60 F254 (Merck). Column chromatography was
performed on Matrex LC 60A (silica gel, 35-70 µm, Grace
Davidson). Because partially decomposition for these highly con-
jugated compounds, the elementary microanalysis are still not sat-
isfactory, despite several attempts (only 0.6 – 0.7% instead 0.4%).
The high resolution mass spectra were obtained at the Laboratoire
de l'Activation Moléculaire of the Ecole Normale Supérieure.
This compound was obtained as a black solid (37%), mp 195-
1
196 °C; H nmr (DMSO-d ): δ 2.16 (s, 3H), 2.30 (s, 3H), 6.13 (m,
1H), 6.68 (s, 1H), 7.29 (dd, 1H, J = 1.0 Hz, J = 8.4 Hz), 7.48 (dd,
1H, J = 1.0 Hz, J = 7.4 Hz), 7.72 (dd, 1H, J = 7.4 Hz, J = 8.4 Hz),
10.98 (s, 1H), 12.11 (s, 1H); ms (isobutane) m/z 268 (MH ); uv
(THF) λmax (lg ε) = 240 (4.10), 292 (3.97), 402 (3.70), 532 (3.49);
ir (KBr) ν 3260 cm- (N-H), 1620 cm (C=O); hrms (FAB) m/z
6
+
1
-1
Organic solutions, after drying with anhydrous MgSO , were con-
centrated at T° < 60 °C under reduced pressure.
4
+
Calcd. for C H NO (MH ): 268.0974; Found: 268.0971.
16
14
3

Jan-Feb 2002
Reaction of 2,5-Dimethylpyrroles with Quinones
129
Methyl 4-(5-Hydroxy-1,4-dioxo-1,4-dihydronaphthalen-3-yl)-
Synthesis of Quinoxaline-5,8-dione (5) [9-15].
2
,5-dimethyl-1H-pyrrol-2-yl-carboxylate (9b).
a) Nitration of 1,4-dimethoxybenzene leads a mixture of 2,3-
and 2,5-dinitro-1,4-dimethoxybenzene (ratio 18/81) which by
reduction and reaction with glyoxal leads to 5,8-
dimethoxyquinoxaline.
b) The reduction of the above mixture of dinitro-1,4-
dimethoxybenzenes by tin in concentrated HCl following the
described method [12] gives after reaction with glyoxal 5,8-
dimethoxyquinoxaline in 47% yield on the basis of 2,5-dinitro-
1,4-dimethoxybenzene. Catalytic reduction by hydrogen [11]
affords only 34% yield of the same 5,8-dimethoxyquinoxaline,
mp 150-151 °C. Lit. [11]: 150-151 °C, but the product is easier to
isolate.
This compound was obtained as a orange solid (31%), mp 182-
1
1
6
1
83 °C; H nmr (CDCl ): 2.18 (s, 3H), 2.49 (s, 3H), 3.64 (s, 3H),
.74 (s, 1H), 7.23-7.30 (m, 1H), 7.62-7.66 (m, 2H), 8.55 (s, 1H),
2.11 (s, 1H); ms (isobutane) m/z 325 (M ); uv (THF) λ
3
+
(lg
max
-
1
ε) = 244 (4.04), 259 (4.04), 412 (3.58); ir (KBr) ν 3260 cm (N-
H), 1635, 1670 cm (C=O, quinone), 1725 cm (C=O, ester);
hrms (FAB) m/z Calcd. for C18H16NO5 (MH ): 326.1028;
Found: 326.1027.
-1
-1
+
2
-(1,2,5-Trimethyl-1H-pyrrol-3-yl)-5-hydroxy-1,4-naphtho-
quinone (9c).
This compound was obtained as a black solid (33%), mp 181-
c) Oxidative demethylation by CAN. The above 5,8-
dimethoxyquinoxaline (26.3 mmoles, 5 g) in acetonitrile (100
mL) was stirred for one hour with CAN (66.7 mmoles, 36.15 g).
Extraction by chloroform (3 X 100 mL) leads to compound (5,
3.12 g, 74%), mp 172-173 °C. Lit. [11]: 172-173 °C.
1
1
6
1
82 °C; H nmr (CDCl ): 2.26 (s, 3H), 2.33 (s, 3H), 3.46 (s, 3H),
3
.20 (s, 1H), 6.74 (s, 1H), 7.22-7.29 (m, 1H), 7.61-7.65 (m, 2H),
+
2.32 (s, 1H); ms (isobutane) m/z 282 (MH ); uv (THF) λmax (lg
ε) = 240 (3.88), 290 (3.66), 406 (3.49), 521 (3.21); ir (KBr) ν
-
1
1
(
630 cm (C=O); hrms (FAB) m/z Calcd. for C17H16NO3
General Method for the Synthesis of 6-Pyrrolylquinoline-5,8-
diones (12a-12d) and 6-Pyrrolylquinoxaline-5,8-diones (13a-
13d).
+
MH ): 282.1130; Found: 282.1136.
Methyl 4-(5-Hydroxy-1,4-dioxo-1,4-dihydronaphthalen-3-yl)-
1,2,5-trimethyl-1H-pyrrol-2-yl-carboxylate (9d).
A solution of FeCl •6H O (3.14 mmoles, 912 mg) in water (48
3
2
mL) and acetic acid (12 mL) was stirred with 3.14 mmoles of
quinoline-5,8-dione (4) or quinoxaline-5,8-dione (5) and 12.58
mmoles of pyrrole (7) in chloroform (50 mL). The reaction was
followed by tlc; the mixture was isolated as above.
This compound was obtained as a orange solid (26%), mp 172-
1
1
3
1
74 °C; H nmr (CDCl ): 2.22 (s, 3H), 2.54 (s, 3H), 3.48 (s, 3H),
3
.59 (s, 3H), 6.72 (s, 1H), 7.24-7.30 (m, 1H), 7.62-7.75 (m, 2H),
+
2.10 (s, 1H); ms (isobutane) m/z 339 (M ); uv (THF) λmax (lg
-
ε) = 242 (3.79), 264 (3.76), 409 (3.24); ir (KBr) ν 1640, 1660 cm
6
-(4-Carbomethoxy-2,5-dimethylpyrrol-3-yl)quinoline-5,8-
1
-1
(
C=O, quinone), 1705 cm (C=O, ester); hrms (FAB) m/z
dione (12b).
+
Calcd. for C H NO (MH ): 340.1185; Found: 340.1201.
19
18
5
This compound was obtained as a black solid (19%), mp
Synthesis of Compounds (10 and 11).
1
2
20-221 °C; H nmr (CDCl ): δ 2.25 (d, 3H, J = 0.7 Hz), 2.34
3
(
7
s, 3H), 3.46 (s, 3H), 6.22 (d, 1H, J = 0.7 Hz), 6.97 (s, 1H),
.66 (dd, 1H, J = 7.9 Hz, J = 4.7 Hz), 8.47 (dd, 1H, J = 7.9 Hz,
Methyl 4-(1,2-Dioxo-1,2-dihydronaphthalen-4-yl)-2,5-dimethyl-
1
H-pyrrol-3-yl-carboxylate (10).
1
3
J = 1.7 Hz), 9.03 (dd, 1H, J = 4.7 Hz, J = 1.7 Hz); C nmr
CDCl ): 12.4, 12.6, 30.7, 108.2, 112.6, 127.1, 129.5, 129.6,
A solution of pyrrole (7b, 3.27 mmoles, 500 mg) and 1,2-naph-
(
1
3
thoquinone (3, 6.53 mmoles, 1.033 g) in absolute ethyl alcohol
50 mL) was stirred with a trace of p-toluenesulfonic acid for three
31.1, 131.2, 134.9, 144.1, 147.8, 154.2, 183.6, 185.2; ms (70
(
+
.
eV) m/z 266 (M ); uv (THF) λmax (lg ε) = 250 (4.12), 293
(
(C=O); hrms (FAB) m/z Calcd. for C16H15N O (MH ):
2
hours. In the same way as above, compound (10, 724 mg, 72%) is
-1
3.87), 382 (3.32), 510 (3.51); ir (KBr) ν 1650, 1670 cm
1
obtained as a red solid, mp 176-179 °C; H nmr (CDCl ): δ 2.20
+
3
2
2
(s, 3H), 2.57 (s, 3H), 3.48 (s, 3H), 6.33 (s, 1H), 7.23 (m, 1H), 7.44-
67.1134; Found: 267.1133.
7
3
.61 (m, 2H), 8.11-8.17 (m, 1H), 8.72 (s, 1H); ms (ammonia) m/z
+
+
6-(1,2,5-Trimethylpyrrol-3-yl)quinoline-5,8-dione (12c).
27 (MNH4 ), 310 (MH ); uv (THF) λ
(lg ε) = 246 (4.12), 315
max
-
1
-1
(3.42), 398 (3.23); ir (KBr) ν 3280 cm (N-H), 1650, 1690 cm
This compound was obtained as a red solid (59%), mp 237-241
-1
(C=O, quinone), 1735 cm (C=O, ester); hrms (FAB) m/z Calcd.
1
°
C; H nmr (CDCl ): δ 2.25 (s, 3H), 2.52 (s, 3H), 3.63 (s, 3H),
3
+
for C H NO (MH ): 310.1079; Found: 310.1069.
18
16
4
6.94 (s, 1H), 7.70 (dd, 1H, J = 7.9 Hz, J = 4.7 Hz), 8.48 (dd, 1H,
J = 7.9 Hz, J = 1.7 Hz), 9.05 (dd, 1H, J = 4.7 Hz, J = 1.7 Hz); ms
Methyl 4-(1,2-Dioxo-1,2-dihydronaphthalen-4-yl)-1,2,5-
trimethyl-1H-pyrrol-3-yl-carboxylate (11).
.
+
(
(
(
70 eV) m/z 310 (M ); uv (THF) λ
3.66), 462 (3.17); ir (KBr) ν 3360 cm (N-H), 1660, 1670 cm
C=O, quinone), 1705 cm (C=O, ester); hrms (FAB) m/z Calcd.
(lg ε) = 240 (4.21), 288
max
-
1
-1
As above, pyrrole (7d, 2.99 mmoles, 500 mg) and 1,2-naphtho-
-1
quinone (3, 6 mmoles, 950 mg), give compound (11, 606 mg, 65%)
+
for C H N O (MH ): 313.1188; Found: 313.1184.
1
7 17 2 4
1
as a red solid, mp 188-189 °C; H nmr (CDCl ): δ 2.17 (s, 3H), 2.58
3
6
-(4-Carbomethoxy-1,2,5-trimethylpyrrol-3-yl)quinoline-5,8-
(s, 3H), 3.40 (s, 3H), 3.51 (s, 3H), 6.27 (s, 1H), 7.15-7.19 (m, 1H),
dione (12d).
7
.38-7.53 (m, 2H), 8.09-8.13 (m, 1H); ms (ammonia) m/z 324
+
(MH ); uv (THF) λ
(lg ε) = 248 (4.26), 330 (3.42), 398 (3.26); ir
This compound was obtained as a red solid (22%), mp 171-172
max
-1
-1
1
(KBr) ν 1660, 1690 cm (C=O, quinone), 1720 cm (C=O, ester).
°C; H nmr (CDCl ): δ 2.19 (s, 3H), 2.49 (s, 3H), 3.45 (s, 3H),
3
3
8
.55 (s, 3H), 6.86 (s, 1H), 7.66 (dd, 1H, J = 7.9 Hz, J = 4.7 Hz),
Synthesis of Quinoline-5,8-dione (4).
.42 (dd, 1H, J = 7.9 Hz, J = 1.7 Hz), 9.00 (dd, 1H, J = 4.7 Hz, J =
+
Quinone (4) is obtained by the method described in the litera-
ture [7] from 8-hydroxyquinoline in three steps (yield: 29%), mp
1.7 Hz); ms (ammonia) m/z 325 (MH ); uv (THF) λ
240 (4.38), 286 (3.79), 456 (3.14); ir (KBr) ν 1660, 1670 cm
(C=O, quinone), 1700 cm- (C=O, ester).
(lg ε) =
max
-1
1
121-122 °C. Lit. [7]: 121-122 °C.

1
6
30
C. Lion, R. Baudry, M. Hedayatullah, L. Da Conceição, S. Genard and J. Maignan
Vol. 39
-(4-Carbomethoxy-2,5-dimethylpyrrol-3-yl)quinoxaline-5,8-
[4] R. Mölhau and A. Redlich, Ber., 44, 3605 (1911).
[5] A. Pieroni and V. Veremenco, Gazz. Chim. Ital., 66, 455
1926).
6] H. Fischer, A. Treibs and E. Zaucker, Justus Liebigs Ann.
Chem., 92, 2026 (1959).
7] M. Matsuoka, H. Soejima and T. Kitao, Dyes and
Pigments, 16, 309 (1991).
8a] Y. T. Pratt and N. L. Drake, J. Am. Chem. Soc., 82, 1155
1960); [b] H. J. Teuber and N. Götz, Ber., 87, 1236 (1954).
9] F. E. King, N. G. Clark and P. M. H. Davis, J. Chem. Soc.,
3012 (1949).
dione (13b).
(
This compound was obtained as a red solid (44%), mp 209-210
[
1
°C; H nmr (CDCl ): δ 2.27 (s, 3H), 2.51 (s, 3H), 3.65 (s, 3H),
3
7.00 (s, 1H), 8.36 (s, 1H), 9.05 (m, 2H); ms (ammonia) m/z 312
[
+
(MH ); uv (THF) λ
(lg ε) = 251 (4.26), 286 (3.91), 330 (3.60),
max
-1
468 (3.25); ir (KBr) ν 1655, 1690 cm (C=O, quinone), 1705
[
-
1
cm (C=O, ester); hrms (FAB) m/z Calcd. for C16H14N O
3
4
(
+
(MH ): 312.0984; Found: 312.0990.
[
6-(1,2,5-Trimethylpyrrol-3-yl)quinoxaline-5,8-dione (13c).
[
[
10] R. Nietzki and F. Rechberg, Ber., 23, 1211 (1890).
11] J. D. Warren, V. J. Lee and R. B. Angier, J. Heterocyclic
This compound was obtained as a red solid (56%), mp 196-197
1
°
(
C; H nmr (CDCl ): δ 2.26 (s, 3H), 2.36 (s, 3H), 3.47 (s, 3H), 6.26
3
Chem., 79, 1617 (1979).
12] F. Outurquin and C. Paulmier, Bull. Soc. Chim. Fr., 153
1983).
13] J. Adachi, Nippon Kagaku Zasshi, 76, 311 (1955); Chem.
+
s, 1H), 7.04 (s, 1H), 9.01 (m, 2H); ms (ammonia) m/z 268 (MH );
[
uv (THF) λmax (lg ε) = 248 (4.23), 282 (4.23), 349 (3.92), 519
(
-1
(
3.73); ir (KBr) ν 1640, 1690 cm (C=O, quinone); hrms (FAB)
[
+
m/z Calcd. for C H N O (MH ): 268.1086; Found: 268.1088.
1
5 14 3 2
Abstr., 51, 17936 (1957).
6
-(4-Carbomethoxy-1,2,5-trimethylpyrrol-3-yl)quinoxaline-5,8-
[14a] P. Jacob III, P. S. Callery, A. T. Shulgin and N.
Castagnoli, J. Org. Chem., 41, 3627 (1976); [b] A. Palmgren, A.
Thorarensen and J. E. Bäckvall, J. Org. Chem., 63, 3764 (1998).
dione (13d).
This compound was obtained as a red solid (61%), mp 235-237
[
15] P. R. Brooks, M. C. Wirtz, M. G. Vetelino, D. M. Rescek,
G. F. Woodworth, B. P. Morgan and J. W. Coe, J. Org. Chem., 64,
719 (1999).
16a] Y. Tanoue, A. Terada, K. Sakata, M. Hashimoto, S.-I.
Morishita, M. Hamada, N. Kai and T. Nagai, Bull. Chem. Soc. Jpn.,
7, 2886 (1994); [b] Y. Tanoue, A. Terada, H. Taniguchi, T. Okuma,
1
°C; H nmr (CDCl ): δ 2.26 (s, 3H), 2.54 (s, 3H), 3.50 (s, 3H),
3
3.62 (s, 3H), 6.97 (s, 1H), 9.04 (m, 2H); ms (ammonia) m/z 326
9
+
(MH ); uv (THF) λ
(lg ε) = 251 (4.23), 277 (4.09), 324 (3.70),
max
[
-1
4
64 (3.21); ir (KBr) ν 1662, 1690 cm (C=O, quinone), 1708
-
1
cm (C=O, ester); hrms (FAB) m/z Calcd. for C17H16N O
3
4
6
+
(MH ): 326.1141; Found: 326.1138.
H. Kaai, M. Anan, Y. Kakara, M. Doi and S.-I. Morishita, Bull.
Chem. Soc. Jpn., 66 , 3712 (1993).
REFERENCES AND NOTES
[17a] G. Cassillo, G. J. Ellames, A. G. Osborne and P. G.
Sammes, J. Chem. Res. (M), 836 (1978); [b] S. Laugraud, A.
Guingant, C. Chassagnard and J. d'Angelo, J. Org. Chem., 53, 1557
[
1a] C. Lion, R. Baudry, M. Hedayatullah, L. Da Conceição,
M. Hocquaux, S. Genard and J. Maignan, J. Heterocyclic Chem., 37,
635 (2000) and references therein; [b] R. Baudry, J. Maignan and
S. Genard, Eur. Pat. Appl. EP 984 010 A , Cl07D 401/04
(
1988); [c] G. Barre, M. Hocquaux, B. Jacquet, M. deMin, M. T.
Maurette and E. Oliveros, Tetrahedron Lett., 27, 6197 (1986).
18] K. Yoshida, Y. Ueno, M. Suzuki, Y. Yoshida and Y. Kubo,
1
[
1
(
(
(
08.25.1999); Chem. Abstr., 132, 212504 (2000).
2] R. Baudry, PhD Thesis, University of Paris 7 (France)
1998).
J. Chem. Soc., Perkin Trans. 1, 2715 (1992).
[19] P. Ibison, P. J. S. Foot and J. W. Brown, Synth. Met., 76,
297 (1996).
[20] K. Yoshida, M. Ishiguro, H. Honda, M. Yamamoto and Y.
Kubo, Bull. Chem. Soc. Jpn., 61, 4335 (1988).
[
[
3] K. Yoshida, Y. Yoshida and Y. Kubo, Chem. Exp., 10, 749
1990).