Polystyrene-supported iodobenzene diacetate (PSIBD)-mediated synthesis of 1,2-diacylbenzenes from 2-hydroxyaryl aldehyde/ketone acylhydrazones

Article abstract of DOI:10.1080/00397910802213752

Synthesis of some new 1,2-diacylbenzenes is described by the oxidation of 2-hydroxyaryl aldehyde/ketone acylhydrazones using polystyrene-supported iodobenzene diacetate (PSIBD) in good yield. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802213752

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Polystyrene-Supported
Iodobenzene Diacetate
(PSIBD)–Mediated Synthesis of
1,2-Diacylbenzenes from 2-
Hydroxyaryl Aldehyde/Ketone
Acylhydrazones
Sunil Kumar a & Devinder Kumar a
a Department of Chemistry , Guru Jambheshwar
University of Science and Technology , Hisar, India
Published online: 14 Oct 2008.
To cite this article: Sunil Kumar & Devinder Kumar (2008) Polystyrene-Supported
Iodobenzene Diacetate (PSIBD)–Mediated Synthesis of 1,2-Diacylbenzenes from
2-Hydroxyaryl Aldehyde/Ketone Acylhydrazones, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:21,
3683-3699, DOI: 10.1080/00397910802213752
To link to this article: http://dx.doi.org/10.1080/00397910802213752
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Synthetic Communications1, 38: 3683–3699, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802213752
Polystyrene-Supported Iodobenzene Diacetate
(PSIBD)–Mediated Synthesis of
1,2-Diacylbenzenes from 2-Hydroxyaryl
Aldehyde/Ketone Acylhydrazones
Sunil Kumar and Devinder Kumar
Department of Chemistry, Guru Jambheshwar University of Science and
Technology, Hisar, India
Abstract: Synthesis of some new 1,2-diacylbenzenes is described by the oxidation
of 2-hydroxyaryl aldehyde=ketone acylhydrazones using polystyrene-supported
iodobenzene diacetate (PSIBD) in good yield.
Keywords: 1,2-Diacylbenzenes, 2-hydroxyaryl aldehyde=ketone acylhydrazones,
polystyrene-supported iodobenzene diacetate (PSIBD)
INTRODUCTION
1,2-Diacylbenzenes are important molecules because of their potential to
serve as starting materials in organic synthesis.[1] The presence of two car-
bonyl groups ortho to each other at the benzene ring allows the formation
of novel heterocycles as well as other nonheterocyclic aromatic com-
pounds. For example, 1,2-diacylbenzenes have proven to be useful pre-
cursors to isoquinolines,[2] isoindoles,[3] imidazo[2,1-a]isoindoles,[4] N-
arylphthalimidines,[5,6] and 1,3-diphenyl-2-nitroindene.[7] 1,2-Diacylbenzenes
have been of interest as fluorescence reagents for high-sensitivity detec-
tion and quantitative measurements of biological compounds bearing a
primary amino group, such as amino acids and peptides.[8] They have
Received March 19, 2008.
Address correspondence to Devinder Kumar, Department of Chemistry, Guru
Jambheshwar University of Science and Technology, Hisar 125001, India. E-mail:
dk_ic@yahoo.com
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S. Kumar and D. Kumar
also been used for a highly specific thin-layer chromatography (TLC)-
fluorescent detection of oxazepam and lorazepam.[9] Diacetylbenzene,
in particular, was used in a fluorometric assay for biotinase because of
its ability to react selectively with lysine.[10]
There are several methods for the preparation of 1,2-diacylbenzenes
such as oxidation of benzhydrols with selenium dioxide[4] and o-hydro-
xyaryl ketone acylhydrazones with lead tetraacetate[11] or hypervalent
iodine reagents.[12,13] Synthesis of 1,2-diacylbenzenes from 2-hydroxyaryl
aldehyde=ketone acylhydrazones is significant, because a wide variety of
functionalized 1,2-diacylbenzenes can be obtained from inexpensive and
easily prepared starting materials in high yield under mild reaction
conditions. The polystyrene-supported reagent to be utilized for the
transformation of 2-hydroxyaryl aldehyde=ketone acylhydrazones to
1,2-diacylbenzenes is nontoxic, inexpensive, and readily available. More-
over, the by-product iodopolystyrene, generated in situ, can be easily
recycled.
Recently hydrazone derivatives have been demonstrated to possess
various types of biological activities (antimicrobial, anticonvulsant, anti-
depressant, analgesic, anti-inflammatory, antimalarial, antiviral, anti-
platelet, antitubercular and antitumoral activities).[14] Hydrazones
possessing an azomethine proton (–NHN¼CH–) constitute an important
class of compounds for new drug development.[14]
RESULTS AND DISCUSSION
Commercially available 2-hydroxyaryl aldehyde=ketones (1) and isonico-
tinic acid hydrazide, benzoic acid hydrazide, 4-toluic acid hydrazide, or
acetic acid hydrazide (2) were refluxed together in n-propanol to prepare
the 2-hydroxyaryl aldehyde=ketone acylhydrazones (3), which were used
without further purification. In a typical oxidation procedure, 2-hydro-
xyaryl aldehyde=ketone acylhydrazones (3) in dichloromethane was stir-
red with a slight excess of polystyrene-supported iodobenzene diacetate
(PSIBD) at 40ꢀC (Scheme 1). A mild effervescence (evolution of N2)
was generally observed upon addition of oxidant. The products were
purified by percolation through a column of silicagel using hexane–
ethyl acetate as eluent.
Hydrazones can exist as four isomers because of the geometric
isomerism with respect to the imino group (E, Z isomers) and rotational
isomerism as a result of hindered rotation about the amide linkage (anti-
syn conformers). X-ray spectroscopic analysis revealed that in the solid
state acyl and aroylhydrazones form only E-isomers.[15] It was also
demonstrated that in the solid state acylhydrazones of benzaldehyde

PSIBD-Mediated Synthesis of 1,2-Diacylbenzenes
3685
Scheme 1. Synthesis of the 3a–k and 4a–k.
form syn-conformers that aggregate to centrosymmetric dimers because
of their intermolecular hydrogen bonding. Only syn-E isomers possess
C¼O and N–N groups in a trans-conformation that permits the forma-
tion of dimers. It was also shown that aroylhydrazones form only the
anti-conformer, both in the solid state[15] and in solution.[16]
The hydrazones in the present study were thoroughly analyzed by
NMR, which showed that most of the hydrazones (3a–e and 3h–k) form
only the E-isomer, with the anti-conformer in solution (DMSO-d6).
Table 1 revealed that in hydrazones 3a–e and 3h–k the OH and NH pro-
ton resonated at d 12.09–13.26 and 10.20–11.40, respectively, indicating
thereby the existence of intramolecular hydrogen bonding having the
anti-E conformation. On the other hand, the hydrazones 3f, g also form
an E-isomer, but with both anti- and syn-conformers (Fig. 1). Analysis of
1H NMR spectrum of 3g demonstrated that OH is represented by two
signals at d 12.13 and 13.28. The possible reason for such splitting is par-
ticipation of the part of the 2-hydroxy group proton in an intramolecular
hydrogen bond with the nitrogen atom of the imino group. There were
also two signals from the NH proton at d 9.97 and 10.31. The percentage
of anti-conformer, calculated from the intensities of the corresponding
signals, possessing a hydroxy group that form intramolecular hydrogen

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S. Kumar and D. Kumar
Figure 1. Anti- and syn-conformers of 3g.
bond, is slightly larger than the syn-conformer, which lacks the possibility
of forming such bond.
The E-configuration of hydrazones may also be explained on the
basis of a signal attributed to methyl=ethyl groups (R2) in 13C NMR
spectra. The methyl signal appeared at d 13.2–13.7 and ethyl signal at
d 10.5–11.0 (CH3) and 18.6–19.2 (CH2) (Fig. 2).
This finding is analogous with the 13C NMR spectra of hydrazones in
which one methyl group resonated more at the upper field in one isomer
than in the other (17.7 vs 24.0 ppm), probably due to a sterically upfield
shift (Fig. 3).[17]
Figure 2. Chemical shifts of methyl=ethyl protons in 3.
Figure 3. Chemical shifts of methyl carbon in E and Z isomers.

PSIBD-Mediated Synthesis of 1,2-Diacylbenzenes
3689
It was also observed that hydrazones with electron-donating
substituents at R1 (3h–j) react relatively faster than hydrazones with
electron-withdrawing substituents at R1 (3a–e). The reaction also shows
a large rate dependence on substituents at R2. With R2 ¼ H (3h), the reac-
tion proceeded to completion in 1 h, whereas with R2 ¼ Et (3d, 3g) the
reaction took 12 h. The ethyl group at R2 may sterically hinder the
approach of the acetate anion at the hydrazone carbon (see mechanism).
1H NMR spectra of compounds 4a, b, e, f, i, and k show a singlet at
d 2.49–2.51 for the acetyl group. The triplet at d 1.08 and quartet at
d 2.80–2.95 with J ¼ 7.2 Hz in the 1H NMR spectra of 4d, g, and j results
from the ethyl group. 13C NMR spectra of 1,2-diacylbenzenes show two
characteristic signals at d 196.2–201.7 for two carbonyl groups. The car-
1
bonyl signals for 2-acyl benzaldehydes were at d 161.4–165.0. The H
NMR and 13C NMR spectra of 1,2-diacylbenzenes (4) are given in the
Tables 2 and 3 respectively.
1,2-Diacylbenzenes (4) exhibit rotational isomerism and may exist in
four forms (Fig. 4). Analysis of NMR data indicates that form I and III
do not exist; form II and IV are present in solution. Compounds 4a–b,
4d–e, 4g, and 4i–k (where R1 ¼ 4-pyridyl, 4-tolyl and phenyl and
R2 ¼ Me and Et) exist as rotational isomer II instead of IV, because
H-6 resonated at d 7.8 in comparison to H-3, which appeared at d 7.3.
Further, compounds 4c and 4h (where R1 ¼ 4-pyridyl and 4-tolyl and
R2 ¼ H) also exist as rotational isomer II because H-6 resonated at
d 7.8 in comparison to H-3, which appeared at d 7.1, probably shielded
as a result of the anisotropy of R1 groups. Additionally, this shielding
may also be due to the different orientation achieved by R2 groups, where
R2 ¼ H instead of Me or Et. However, compound 4f (where R1 ¼
1
R2 ¼ Me) exists as rotational isomer IV as indicated by H NMR signals
for H-6 and H-3, which appeared at d 7.46 and d 7.63, respectively. This
is probably because the two groups are identical; therefore 4f can adopt
either conformation II or IV.
The possible mechanism of this reaction may follow a route similar
to that proposed by Katritzky[18] with lead tetraacetate. The reaction
begins with ligand exchange of the 2-hydroxyaryl aldehyde=ketone
acylhydrazones (3) with an acetate group on polystyrene-supported
iodobenzene diacetate (PSIBD) to produce intermediate 5. The reductive
elimination of iodopolystyrene is accompanied by the intramolecular
migration of the acetate group to the hydrazone carbon, giving the azoa-
cetate (6), which then give 1,3,4-oxadiazoline (7), followed by cyclization
and loss of acetic acid to give 1,3-dioxane intermediate (8). Elimination of
nitrogen with formation of epoxide then gives intermediate 9, which
undergoes electrocyclic rearrangement to form the 1,2-diacylbenzenes
(4) (Scheme 2).

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S. Kumar and D. Kumar
Figure 4. Rotational isomers of 4.
EXPERIMENTAL
Melting points were determined in open capillaries and are uncorrected.
FTIR spectra were obtained in KBr on Shimadzu FTIR 8210 PC and
Perkin-Elmer Spectrum RX1 instruments and are reported in cen-
.
timetersꢁ1 1H and 13C NMR spectra were determined on a Bruker
Avance II NMR spectrometer operating at 400 MHz and 100 MHz,
respectively, in CDCl3=DMSO-d6 and are expressed as parts per million
(ppm) with respect to TMS. 2-D NMR (correlation spectroscopy [COSY]
and heteronuclear single-quantum coherence [HSQC]) spectra were also
recorded for a few samples. Elemental analysis was carried out on a
Perkin-Elmer 2400 instrument. 2-Hydroxyaryl aldehydes and ketones
and acid hydrazides were purchased from Aldrich.
Scheme 2. Mechanism for the synthesis of 4a–k.

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S. Kumar and D. Kumar
Preparation of 2-Hydroxyaryl Aldehyde/Ketone Acylhydrazones (3)
2-Hydroxyaryl aldehyde=ketone (10.0 mmol) was added to a solution of
acid hydrazide (10.0 mmol) in n-propanol (50 ml), and the solution was
heated to reflux for 6–8 h. The solid obtained was filtered to afford
2-hydroxyaryl aldehyde=ketone acylhydrazones (3), which were used
without further purification.
Data
Isonicotinic Acid [1-(2-Hydroxyphenyl)-ethylidine]-hydrazide (3a)
Yield 75%; mp 240ꢀC (lit.[11a] mp 240–244ꢀC); IR (cmꢁ1): 3432, 3238,
1679, 1610, 1535, 1492, 1452, 1409, 1282, 1240, 1147, 1064, 831, 763;
13C NMR (DMSO-d6) d: 13.6, 117.3, 117.9, 118.6, 121.4, 127.5, 131.0,
139.9, 149.6, 158.9, 159.4, 162.4.
Isonicotinic Acid [1-(2-Hydroxy-5-methylphenyl)-ethylidine]-
hydrazide (3b)
Yield 70%; mp 230ꢀC; IR (cmꢁ1): 3440, 3170, 2920, 1674, 1600, 1535,
1480, 1410, 1362, 1320, 1290, 1230, 1150, 1100, 1058. Anal. calcd for
C15H15N3O2: C, 66.90; H, 5.61; N, 15.60%. Found: C, 66.92; H, 5.58;
N, 15.63%.
Isonicotinic Acid (2-Hydroxybenzylidine)-hydrazide (3c)
Yield 80%; mp 253–54ꢀC; IR (cmꢁ1): 3428, 3174, 3008, 2842, 1683, 1617,
1566, 1490, 1407, 1390, 1355, 1290, 1274, 1157, 1066, 850, 771; 13C NMR
(DMSO-d6) d: 116.3, 117.2, 118.7, 121.0, 130.2, 131.1, 139.6, 149.7, 150.7,
157.9, 161.1. Anal. calcd. for C13H11N3O2: C, 64.72; H, 4.60; N, 17.72%.
Found: C, 64.70; H, 4.63; N, 17.65%.
Isonicotinic Acid [1-(2-Hydroxyphenyl)-propylidene]-hydrazide (3d)
Yield 85%; mp 248ꢀC; IR (cmꢁ1): 3410, 3186, 3047, 2981, 1681, 1600,
1525, 1488, 1450, 1406, 1263, 1147, 1058, 827, 775; 13C NMR (DMSO-
d6) d: 11.0, 19.2, 117.3, 117.5, 118.0, 121.7, 127.3, 130.9, 140.1, 149.5,
159.4, 162.2, 162.9. Anal. calcd. for C15H15N3O2: C, 66.90; H, 5.61;
N, 15.60%. Found: C, 66.93; H, 5.64; N, 15.60%.

PSIBD-Mediated Synthesis of 1,2-Diacylbenzenes
3695
Isonicotinic Acid [1-(5-Chloro-2-hydroxyphenyl)-ethylidine]-hydrazide (3e)
Yield 82%; mp 242ꢀC; IR (cmꢁ1): 3448, 3230, 2923, 1670, 1602, 1546,
1479, 1413, 1365, 1325, 1294, 1230, 1155, 1107, 1068, 817, 756; 13C
NMR (DMSO-d6) d: 13.7, 99.4, 121.5, 122.3, 126.9, 130.6, 149.6, 157.5,
162.7. Anal. calcd. for C14H12ClN3O2: C, 58.04; H, 4.17; N, 14.50%.
Found: C, 58.00; H, 4.10; N, 14.45%.
Acetic Acid [1-(5-Chloro-2-hydroxyphenyl)-ethylidine]-hydrazide (3f)
Yield 88%; mp 228–229ꢀC; IR (cmꢁ1): 3402, 3186, 3101, 2927, 1676,
1596, 1467, 1388, 1342, 1309, 1282, 1232, 1161, 1016, 833, 765. Anal.
calcd. for C10H11ClN2O2: C, 52.99; H, 4.89; N, 12.36%. Found: C,
52.90; H, 4.93; N, 12.30%.
Acetic Acid [1-(2-Hydroxyphenyl)-propylidene]-hydrazide (3g)
Yield 78%; mp 194ꢀC; IR (cmꢁ1): 3390, 3249, 3039, 2970, 1666, 1606,
1525, 1490, 1473, 1452, 1377, 1336, 1305, 1265, 1215, 1062, 1020, 860,
761; 13C NMR (DMSO-d6) d: 10.2, 10.6, 18.6, 18.7, 20.6, 20.8, 117.0,
117.41, 117.48, 117.5, 117.7, 118.5, 126.7, 127.0, 130.4, 130.6, 156.4,
157.7, 158.2, 159.2, 166.2, 171.8. Anal. calcd. for C11H14N2O2: C,
64.06; H, 6.84; N, 13.58%. Found: C, 64.10; H, 6.80; N, 13.50%.
4-Methylbenzoic Acid (2-Hydroxybenzylidine)-hydrazide (3h)
Yield 80%; mp 202–203ꢀC; IR (cmꢁ1): 3413, 3218, 3047, 2916, 1650,
1623, 1610, 1571, 1488, 1367, 1305, 1288, 1195, 1149, 1072, 877, 738.
Anal. calcd. for C15H14N2O2: C, 70.85; H, 5.55; N, 11.02%. Found: C,
70.80; H, 5.60; N, 11.00%.
4-Methylbenzoic Acid [1-(5-Chloro-2-hydroxyphenyl)-ethylidine]-
hydrazide (3i)
Yield 76%; mp 240ꢀC; IR (cmꢁ1): 3416, 3265, 1645, 1604, 1562, 1519,
1469, 1379, 1325, 1290, 1230, 1184, 1159, 1118, 1103, 902, 881, 835,
817, 744. Anal. calcd. for C16H15ClN2O2: C, 63.47; H, 4.99; N, 9.25%.
Found: C, 63.40; H, 5.02; N, 9.30%.

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S. Kumar and D. Kumar
4-Methylbenzoic Acid [1-(5-Chloro-2-hydroxyphenyl)-
propylidine]-hydrazide (3j)
Yield 65%; mp 176–177ꢀC; IR (cmꢁ1): 3415, 3230, 1631, 1608, 1571,
1527, 1483, 1444, 1276, 1259, 1217, 1178, 1099, 906, 827, 754; 13C
NMR (DMSO-d6) d: 10.5, 18.7, 21.0, 117.4, 117.6, 117.9, 126.9, 127.4,
128.6, 129.7, 130.6, 142.0, 159.4, 159.9, 163.8. Anal. calcd. for
C17H18N2O2: C, 72.32; H, 6.43; N, 9.92%. Found: C, 72.30; H, 6.40;
N, 9.95%.
Benzoic Acid [1-(5-Chloro-2-hydroxyphenyl)-ethylidine]-hydrazide (3k)
Yield 72%; mp 212–214ꢀC; IR (cmꢁ1): 3406, 3222, 1641, 1608, 1577,
1517, 1479, 1460, 1375, 1323, 1288, 1228, 1159, 1107, 1026, 904, 875,
848, 823, 796; 13C NMR (DMSO-d6) d: 13.2, 118.7, 120.0, 122.3, 126.7,
127.6, 127.8, 130.3, 131.4, 132.5, 155.6, 157.5, 164.3. Anal. calcd. for
C15H13ClN2O2: C, 62.40; H, 4.54; N, 9.70%. Found: C, 62.35; H, 4.50;
N, 9.65%.
Preparation of 1,2-Diacylbenzenes (4)
Polystyrene-supported iodobenzene diacetate (PSIBD) (1.5 mmol) was
added to a stirred solution of the 2-hydroxyaryl aldehyde=ketone acylhy-
drazones (3) (1.0 mmol) in dichloromethane (10 ml). After the 3 was con-
sumed (monitored by thin-layer chromatography, TLC), the mixture was
filtered to remove the resin and washed with 5 ml of dichloromethane and
6 ml of water. The aqueous layer was extracted with dichloromethane.
The combined extract was washed with saturated sodium bicarbonate
solution, dried over magnesium sulphate, filtered, and concentrated in
vacuo to give crude 1,2-diacylbenzene. The pure product was isolated
by column chromatography on silica gel (60–120 mesh) using hexane–
ethyl acetate (90:10) as eluent.
Data
1[2-(Pyridine-4-carbonyl)-phenyl]-ethanone (4a)
Yield 85%; mp 114ꢀC (lit.[11a] mp 115–116ꢀC); IR (cmꢁ1): 3034, 1677,
1595, 1567, 1486, 1411, 1364, 1327, 1269, 935.

PSIBD-Mediated Synthesis of 1,2-Diacylbenzenes
3697
1[5-Methyl-2-(pyridine-4-carbonyl)-phenyl]-ethanone (4b)
Yield 78%; mp 124ꢀC; IR (cmꢁ1): 3034, 2920, 1676, 1599, 1558, 1490,
1404, 1356, 1302, 1286, 939. Anal. calcd. for C15H13NO2: C, 75.30; H,
5.48; N, 5.85%. Found: C, 75.25; H, 5.50; N, 5.80%.
2-(Pyridine-4-carbonyl)-benzaldehyde (4c)
Yield 90%; mp 115–116ꢀC; IR (cmꢁ1): 3085, 2166, 1726, 1645, 1549,
1451, 1374, 1347, 1251, 993; Anal. Calcd for C13H9NO2: C, 73.92; H,
4.29; N, 6.63%. Found: C, 73.90; H, 4.25; N, 6.60%.
1[2-(Pyridine-4-carbonyl)-phenyl]-propan-1-one (4d)
Yield 65%; mp 75ꢀC; IR (cmꢁ1): 3077, 2970, 2874, 2908, 1720, 1678, 1593,
1561, 1459, 1405, 1375, 1349, 1275, 1221, 935. Anal. calcd. for C15H13NO2:
C, 75.30; H, 5.48; N, 5.85%. Found: C, 75.28; H, 5.50; N, 5.80%.
1[5-Chloro-2-(pyridine-4-carbonyl)-phenyl]-ethanone (4e)
Yield 70%; mp 78ꢀC; IR (cmꢁ1): 1683, 1591, 1556, 1404, 1359, 1325,
1284, 1251, 1101, 964, 941, 839, 756. Anal. calcd. for C14H10ClNO2:
C, 64.75; H, 3.88; N, 5.30%. Found: C, 64.70; H, 3.80; N, 5.26%.
1-(2-Acetyl-5-chlorophenyl)-ethanone (4f)
Yield 75%; mp 45ꢀC; IR (cmꢁ1): 1687, 1589, 1556, 1481, 1361, 1286,
1230, 1103, 960, 823, 771. Anal. calcd. for C10H9ClO2: C, 61.08; H,
4.61%. Found: C, 61.00; H, 4.60%.
1-(2-Acetylphenyl)-propan-1-one (4 g)
Yield 68%; oil; IR (cmꢁ1): 2979, 2939, 1685, 1595, 1569, 1411, 1357, 1263,
1218, 1068, 1016, 948, 763. Anal. calcd. for C11H12O2: C, 74.98; H,
6.86%. Found: C, 74.90; H, 6.85%.
2-(4-Methylbenzoyl)-benzaldehyde (4h)
Yield 85%; mp 164ꢀC; IR (cmꢁ1): 1625, 1614, 1593, 1544, 1498, 1487,
1400, 1257, 1234, 1180, 1066, 1018, 945, 820, 750. Anal. calcd. for
C15H12O2: C, 80.34; H, 5.39%. Found: C, 80.30; H, 5.40%.

3698
S. Kumar and D. Kumar
1-[5-Chloro-2-(4-methylbenzoyl)-phenyl]-ethanone (4i)
Yield 70%; mp 80–81ꢀC; IR (cmꢁ1): 3039, 2912, 1685, 1660, 1587, 1556,
1407, 1359, 1311, 1288, 1251, 1180, 1149, 1101, 968, 929, 842. Anal. calcd.
for C16H13ClO2: C, 70.46; H, 4.80%. Found: C, 70.40; H, 4.75%.
1-[2-(4-Methylbenzoyl)-phenyl]-prop-1-one (4j)
Yield 66%; mp 86ꢀC; IR (cmꢁ1): 3058, 2970, 1687, 1662, 1604, 1566,
1442, 1407, 1375, 1350, 1313, 1271, 1220, 1151, 954, 929, 831, 773. Anal.
calcd. for C17H16O2: C, 80.93; H, 6.39%. Found: C, 80.90; H, 6.40%.
1-(2-Benzoyl-5-chlorophenyl)-ethanone (4k)
Yield 72%; oil; IR (cmꢁ1): 3010, 2915, 1690, 1665, 1585, 1560, 1405, 1350,
1310, 1280, 1250, 1180, 1150, 1101, 960, 929, 840. Anal. calcd. for
C15H11ClO2: C, 69.64; H, 4.29%. Found: C, 69.59; H, 4.30%.
REFERENCES
1. Kotali, A.; Lafazanis, I. S.; Christophidou, A. o-Acylbenzaldehydes in
organic synthesis: A brief review. Arkivoc 2003, 1, 56–58.
2. Hickey, D. M. B.; MacKenzie, A. R.; Moody, C. J.; Rees, C. W. Vinyl azides
in heterocyclic synthesis, part 6: Synthesis of isoquinolines by intramlecular
aza-Wittig reaction. J. Chem. Soc., Perkin Trans. 1 1987, 4, 921–926.
3. Nan’ya, S.; Fujii, T.; Butsugan, Y. J. Isoindole derivatives from o-diacylben-
zenes and aromatic amines. J. Heterocycl. Chem. 1990, 27, 1407–1408.
4. Metlesics, W.; Anton, T.; Chaykovsky, M.; Toome, V.; Sternbach, L. H.
Condensation of o-benzoylbenzaldehyde with aliphatic diamines. J. Org.
Chem. 1968, 33, 2874–2877.
5. Yamamoto, I.; Yanagi, S.; Mamba, A.; Gotah, H. Synthesis of phthalimidines
from aromatic dicarbonyl compounds. J. Org. Chem. 1974, 39, 3924–3929.
6. Yamamoto, I.; Tabo, Y.; Gotah, H.; Minami, T.; Oshiro, Y.; Agawa, T.
The reaction of isocyanate with phthalaldehyde. Tetrahedron Lett. 1971,
25, 2295–2296.
7. Schneider, J.; Evans, E. L.; Fryer, R. I. Synthesis and transformations of
2-nitro-1-phenyl-1-hydroxyindene and its isomer. J. Org. Chem. 1972, 37,
2604–2608.
8. (a) Weygand, F.; Weber, H.; Maekawa, E.; Eberhardt, G. Chem. Ber. 1956,
89, 1994; (b) Roth, M. Fluorescence reaction for amino acids. Anal. Chem.
1971, 43, 880–882; (c) Sternson, L. A.; Stobaugh, J. F.; Repta, A. J. Rational
design and evaluation of improved o-phthalaldehyde-like fluorogenic

PSIBD-Mediated Synthesis of 1,2-Diacylbenzenes
3699
reagents. Anal. Biochem. 1985, 144, 233–246; (d) Baele, S. C.; Savage, J. C.;
Wiesler, D.; Wiedstock, S. M.; Novotny, M. Fluorescence reagents for
high-sensitivity chromatographic measurements of primary amines. Anal.
Chem. 1988, 60, 1765–1769.
9. Troschutz, R.; Heinemann, O.; Reiner, W.; Troschutz, J. On the fluorescence
detection of oxazepam and lorazepam with phthalaldehyde and analogues.
Arch. Pharm. (Weinheim) 1995, 328, 557–563.
10. Ebrahim, H.; Dakshinamurti, K. A fluorometric assay for biotinidase. Anal.
Biochem. 1986, 154, 282–286.
11. (a) Kotali, A.; Tsoungas, P. G. Oxidation of N-aroylhydrazones of o-hydro-
xyaryl ketones with lead (IV) acetate: A facile route to aromatic o-diketones.
Tetrahedron Lett. 1987, 28, 4321–4322; (b) Kotali, A.; Glaveri, U.; Pavlidou,
E.; Tsoungas, P. G. A novel and facile synthesis of 1,2,3-triacylbenzenes.
Synthesis 1990, 12, 1172–1173; (c) Katrizky, A. R.; Kotali, A. Synthesis of
o-acylarylcarboxylic esters: A new replacement of phenolic hydroxyl by a car-
bonyl group. Tetrahedron Lett. 1990, 31, 6781–6784.
12. Moriarty, R. M.; Bergllund, B. A.; Rao, Chander, M. S. Synthesis of 1,2-
diacylbenzenes from o-hydroxyaryl ketone acylhydrazones using [diacetoxy)
iodo]benzene. Synthesis 1993, 3, 318–320.
13. Xian, H.; Qing, Z.; Jizheng, Z. Preparation of 1,2-diacylbenzenes from
o-hydroxyaryl ketone acylhydrazones using cross-linked poly[styrene(iodoso
diacetate)]. Synth. Commun. 2001, 31, 2413–2418.
14. Rollas, S.; Kucukguzel, S. G. Biological activities of hydrazone derivatives.
Molecules 2007, 12, 1910.
15. Litvinov, I. A.; Kataeva, O. N.; Ermolaeva, L. V.; Vagina, G. A.; Troepol’s-
kaya, T. V.; Naumov, V. A. Crystal and molecular structure of aroyl- and
acetylhydrazones of acet- and benzaldehydes. Bull. Acad. Sci. USSR Div.
Chem. Sci. (Engl. Transl.) 1991, 40, 62–67.
16. Palla, G.; Predieri, G.; Domiano, P. Conformational behavior and E=Z
isomerization of N-acyl and N-aroylhydrazones. Tetrahedron 1986, 42,
3649–3654.
17. Inamoto, K.; Katsuno, M.; Yoshino, T.; Arai, Y.; Hiroya, K.; Sakamoto, T.
Synthesis of 3-substituted indazoles and benzoisoxazoles via Pd-catalyzed
cyclization reactions: Application to the synthesis of nigellicine. Tetrahedron
2007, 63, 2695–2711.
18. Katrizky, A. R.; Harris, P. A. Mechanism of the replacement of phenolic
hydroxyl by carbonyl on lead tetraacetate treatment of o-hydroxyaryl ketone
acylhydrazones. J. Org. Chem. 1991, 56, 5049–5051.