3
28 JOURNAL OF CHEMICAL RESEARCH 2011
2
1
22
2730, 1774, 1720, 1648, 1619, 1549 cm−1; 1H NMR (DMSO-d
δ 7.55 (s, 1H, ArH), 7.82 (s, 1H, hetero-H), 7.94–8.0 (m, 2H, ArH)
nitration followed by reduction. The newly synthesised
-(4-phthalhydrazido)-5-aminoimidazole-4-carboxamide(10),
a heterocyclic analogue of luminol, produced chemilumines-
):
6
1
13
and 11.5 (s, 1H); C NMR: δ 113.3, 118.6, 122.4, 124.4, 129.6, 131.1,
134.1, 139.5, 142.3, 166.4, 168.0, 168.2; HRMS: m/z Calcd for
14
cence by reaction with hydrogen peroxide in the presence
of potassium ferricyanide in sodium hydroxide solution (vide
experimental).
The present communication thus recorded a simple, effi-
cient and high yielding solid phase synthesis of luminol and
related compounds. This is the first report on the synthesis of
+
C H N O Na [M+Na] 294.0603. Found 294.0601.
12
9
5
3
1
-(4-Phthalhydrazido)-5-aminoimidazole-4-carboxamide (10): A
mixture of 9 (0.29 g, 1 mmol) and the H–HQ complex (0.30 g) was
ground intimately in a mortar by a pestle. The mixture was then heated
on an oil bath for a period of 10 min at 140–145 °C. The melted mass
which solidified enmasse on cooling was then decomposed with warm
5
-aminoimidazole-4-carboxamide linked to a phthalhydrazido
water (15 mL), filtered and crystallised from DMF-H
2
O to afford 10,
unit as a possible chemiluminescent agent.
yield 0.18 g (60%), m.p. > 300 °C (DMF-H O); IR (KBr): 3014, 2965,
2
−
1
1
2
894, 1660, 1615, 1556, 1492 cm ; H NMR (DMSO-d ): δ 7.74–
6
7
.87 (m, 2H, ArH), 8.07 (s, 2H, ArH and hetero-H) and 11.46 (s, 2H);
C NMR: 105.6, 119.0, 125.2, 127.1, 127.2, 132.7, 152.9, 154.7.
Experimental
13
Melting points were determined in open capillaries and are uncor-
rected. IR spectra were recorded in KBr discs on a Shimadzu FTIR
The resonances at 125.2, 127.2, 132.7 and 154.7 are each believed to
represent two carbons as 10 is relatively flexible molecule compared
to 9; HRMS: m/z Calcd for C H N O Na [M+Na] 309.0712.
Found 309.0716.
8
300 spectrometer. NMR spectra were recorded on a Bruker AV 500
+
12
10
6
3
spectrometer. High resolution mass spectra (HRMS) were performed
on a Waters Q-ToF Micro Y A263 instrument.
14
3
-Nitrophthalimide (3): A mixture of 3-nitrophthalic acid (2)
Light producing reaction (chemiluminesence) of 10
(
2.1 g, 10 mmol), urea (0.6 g, 10 mmol) and acetic acid (8 mL) was
(
i) 10 (40 mg) was dissolved in 2 mL of 3M NaOH solution and
8 mL water to obtain a stock solution-A.
ii) A second stock solution (solution-B) was prepared by mixing
mL of 3% aq. potassium ferricyanide, 4 mL of 3% hydrogen
heated under reflux in an oil bath for 4 h. The resulting solution was
then cooled, allowed to attain r.t and poured onto crushed ice. The
separated solid was filtered, washed with water and recrystallised
from ethyl acetate to give 3 (87%), m.p. 213–214 °C (lit. 213–
1
4
(
peroxide and 30 mL water.
iii) Now, 5 mL of stock solution-A was diluted by adding 35 mL of
water and this diluted solution and solution-B were poured simultane-
ously into an Erlenmeyer flask in the dark with swirling. A blue light
came from the flask and to increase the brilliance gradually small
quantities of alkali and ferricyanide were added.
23
2
15 °C).
-Aminophthalimide (4): 3 (1 g, 5.2 mmol) was added to a suspen-
(
3
sion of iron powder (3 g, 53 mmol) in water (15 mL) containing
ammonium chloride (0.16 g, 3 mmol). The mixture was kept on a
water bath (80–90 °C) for 2 h and allowed to attain r.t and filtered.
The residue was extracted with hot ethanol (3×20 mL). Evaporation
of the solvent afforded 4 in white needles; yield 0.5 g (60%), m.p.
24
We are thankful to the CSIR, New Delhi, for a senior research
fellowship to P.S.R.
2
68–269 °C (lit. 268–270 °C).
Preparation of H–HQ complex: Hydroquinone (4.3 g, 40 mmol)
was dissolved in 15 mL of 20% N H . H O aqueous solution taken in
2
4
2
a 50 mL round bottomed flask. The solution was then heated in an oil
bath maintained at 80–90 °C. On cooling the inclusion complex of
hydrazine-hydroquinone was obtained as colourless crystals. It was
filtered, washed with cold water and dried; yield 4 g, m.p. 162–163 °C
Received 2 February 2011; accepted 27 April 2011
Paper 1100561 doi: 10.3184/174751911X13058077114827
Published online: 11 July 2011
19
(
lit.162 °C).
-Aminophthalhydrazide (luminol, 1a): Hydrazinolysis of 4: (a)
In the solid phase by the H–HQ complex: A mixture of 4 (0.12 g,
.8 mmol) and the H–HQ complex (0.5 g, 3.4 mmol) was taken in a
3
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601, 1491 cm ; H NMR (DMSO-d ): δ 6.88–6.96 (m, 1H), 7.30
6
(
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3
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(
3
0, 2621.
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2
4
-Aminophthalhydrazide (isoluminol, 1b): 1b was obtained by
1
3
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hydrazinolysis of 8 either by fusion with the H–HQ complex in the
solid phase or by refluxing with ethanolic hydrazine hydrate essen-
tially as described above under luminol (1a) in 80% and 55% yields
14
15
16
24
respectively; m.p. > 300 °C ( lit. 331 °C). IR (KBr): 3357, 3127,
1;
1
3
108, 2892, 1659, 1601, 1492 cm− H NMR (DMSO-d ): δ 6.17
6
(
s, 2H), 6.97–7.02 (m, 1H), 7.87–7.91 (m, 1H), 8.05–8.08 (m, 1H),
1.44 (br, s, 2H); C NMR: δ 118.9, 125.3, 127.0, 127.7, 132.3, 152.8,
55.2, 161.9.
1
17 V.S. Rao and K.V.G. Chandra Sekhar, Synth. Commun., 2004, 34, 2153–
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13
1
1
-(4-Phthalimido)-5-aminoimidazole-4-carboxamide (9): A mix-
ture of aminocyanoacetamide (0.5 g, 5 mmol), ethyl orthoformate
0.8 g, 5 mmol) and acetonitrile (10 mL) was heated under reflux on a
1
9
F. Toda, S. Hyoda, K. Okada and K.J. Hirotsu, J. Chem. Soc., Chem.
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(
2
0
A. Belanger, P. Brasserd, S. Laquerre andY. Merand, Can. J. Chem., 1987,
steam bath for 45 min. To the imino ester (6) formed in solution, was
then added 8 (0.8 g, 5 mmol) and the resulting solution was then
refluxed for a further period of 30 min. The dark orange solution was
cooled to r.t and kept in a freezer overnight. The yellow separated
solid was filtered and crystallised from a large volume of ethanol to
afford 9, yield 0.58 g (67%); m.p. 225–226 °C; IR (KBr): 3375, 3308,
6
5, 1392–1396.
21
22
23
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24 H.D.K. Drew and F.H. Pearman, J. Chem. Soc., 1937, 26–33.