Preparation of 1,2-diacylbenzenes from o-hydroxyaryl ketone acylhydrazones using cross-linked poly[styrene(iodoso diacetate)]

Article abstract of DOI:10.1081/SCC-100105117

The 2 percent cross-linked poly[styrene(iodoso diacetate)] was used to synthesis of 1,2-diacylbenzenes, which gave high yields, and could be recycled.

Full text of DOI:10.1081/SCC-100105117

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PREPARATION OF 1,2-DIACYLBENZENES FROM o-
HYDROXYARYL KETONE ACYLHYDRAZONES USING
CROSS-LINKED POLY[STYRENE-(IODOSO DIACETATE)]
Huang Xian a , Zhu Qing a & Zhang Jizheng a
a Chemistry Department, Xixi Campus, Zhejiang University, Hangzhou, 310028, People's
Republic of China
Published online: 09 Nov 2006.
To cite this article: Huang Xian , Zhu Qing & Zhang Jizheng (2001): PREPARATION OF 1,2-DIACYLBENZENES FROM
o-HYDROXYARYL KETONE ACYLHYDRAZONES USING CROSS-LINKED POLY[STYRENE-(IODOSO DIACETATE)], Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:16, 2413-2418
To link to this article: http://dx.doi.org/10.1081/SCC-100105117
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SYNTHETIC COMMUNICATIONS, 31(16), 2413–2418 (2001)
PREPARATION OF 1,2-DIACYLBENZENES
FROM o-HYDROXYARYL KETONE
ACYLHYDRAZONES USING
CROSS-LINKED POLY[STYRENE-
(IODOSO DIACETATE)]
Huang Xian,* Zhu Qing, and Zhang Jizheng
Chemistry Department, Xixi Campus, Zhejiang University,
Hangzhou, 310028, People’s Republic of China
ABSTRACT
The 2% cross-linked poly[styrene(iodoso diacetate)] was used
to synthesis of 1,2-diacylbenzenes, which gave high yields, and
could be recycled.
Phenyliodine diacetate has attracted wide interest in view of its utility
for oxidation and radical reactions.1 As an easily available and stable reagent,
it has many advantages, such as mild reaction conditions, easy handling
and high selectivity.2 But, it also has major shortcomings: the byproduct
iodobenzene is difficult to remove from product and the reagent is difficult
to reuse. The cross-linked poly[styrene(iodoso diacetate)] can solve these
problems. After the reaction, the byproduct cross-linked polyiodostyrene
can be removed from the reaction solution just by filtration, and reused.
*Corresponding author.
2413
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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HUANG, ZHU, AND ZHANG
1,2-Diacylbenzenes are fluorescence reagents for both qualitative
and quantitative high-sensitivity analyses for amines and amino acids.3 They
are also useful precursors to anthraquinone derivatives,4 isoquinolines,5
isoindoles,6 imidazo[2,1,a]isoindoles,7 etc.
There are several methods for the synthesis of 1,2-diacylbenzenes such
as oxidation of benzhydrols with selenium dioxide7 or o-hydroxyaryl ketone
acylhydrazones with lead tetracetate.8 It also can be prepared by oxidation
of o-ethylacetophenone,9 benzofurans10 or by acylating benzene with
o-acetyl-benzoychloride.11 It has been reported that phenyliodine diacetate
could be used to synthesize 1,2-diacylbenzenes in excellent yield.12 There-
fore, we expected that cross-linked poly[styrene(iodoso diacetate)] has reac-
tivity similar to phenyliodine diacetate.
The 2% cross-linked poly[styrene(iodoso diacetate)] was prepared
according to our previous work.13 First, the 2% cross-linked polystyrene
was iodinated with I2/I2O5/H2SO4 to give poly(4-iodostyrene). Elemental
analysis shows that the resin’s functional group is 2.64 mmol/g. The poly-
iodostyrene was then converted to poly[styrene(iodoso diacetate)] by the
treatment with peracetic acid. Iodometry shows that 98.5% of the iodinated
benzene ring had been converted to phenyliodine diacetate. o-Acylphenols 1
and acetic hydrazides 2 were refluxed together in 1-propanol for 19–48 h to
afford o-hydroxyaryl ketone acylhydrazone 3. Then hydrazones 3 was
oxidized by 2% cross-linked poly[styrene(iodoso diacetate)] in CH2Cl2 at
40ꢀC to yield the corresponding 1,2-diacylbenzenes 4 in 58–85% yield
(Scheme 1). The results are shown in Table I.
The possible mechanism of the reaction is as follows (Scheme 2).
The reaction begins with ligand exchange of the o-hydroxyaryl ketone
Scheme 1.

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1,2-DIACYLBENZENES
2415
Table I. Preparation of 1,2-Diacylbenzenes Using Cross-Linked Poly[styrene(iodoso
diacetate)]
Product 4
Yielda
(%)
Time
(h)
R1
R2
R3
R4
P
p-CH3C6H4
m-NO2C6H4
Me
Ph
m-NO2C6H4
p-CH3C6H4
Me
h
Me
H
H
85
6
Me
Me
Me
Me
Me
Me
Me
H
H
H
H
H
H
H
H
H
H
Me
Me
Me
Me
80
63
69
81
60
75
64
5
20
48
9
42
12
18
P
p-CH3C6H4
Me
Me
Ph
P
h
Me
Me
Cl
H
Cl
H
73
85
45
Me
Me
H
Cl
Cl
H
Cl
Cl
H
67
65
68
40
38
5
5.5
6
H
H
H
58
b
h
aIsolated yield.
bBy using 2% cross-linked poly[styrene(iodoso diacetate) recycled for 5 times.
Scheme 2.

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HUANG, ZHU, AND ZHANG
acylhydrazone with an acetate group on phenyliodine diacetate to
produce intermediate 5. After reductive elimination of iodobenzene, the
acetate group undergoes addition to the hydrazone carbon, yielding inter-
mediate 6. Loss of acetic acid gives 7 which cyclizes to 8, and losses N2 to
give the product.
EXPERIMENTAL
1
2% Cross-linked polystyrene was purchased from Aldrich. H-NMR
spectra were recorded at 60 MHZ or a Varian EM-300 spectrometer from a
solution in CDCl3 or CCl4 of the product. Infrared spectra were recorded on
a Perkin Elmer 683 spectrophotometer in KBr with absorption in cmꢁ1. The
2% cross-linked poly[styrene(iodoso diacetate)] was prepared according to
the known literature.13
1
The preparation of o-hydroxyacetophenone acylhydrazones (3a).
Typical procedure: o-Acylphenol 1 (0.68 g, 5 mmol) was added to
a stirred solution of benzoic hydrazide 2 (0.68 g, 5 mmol) in 1-
propanol (25 mL) and the solution was heated to reflux for 6 h.
The solution was filtered to afford the o-hydroyaryl ketone acylhy-
drazone 3a which was used without further purification.
2
The preparation of 1,2-Diacylbenzenes (4a). Typical procedure: 2%
Cross-linked poly[styrene(iodoso diacetate)] 1.5 mmol (0.75 g) was
added to a stirred solution of the o-hydroxy aryl ketone acylhy-
drazones 3a (0.08 g, 0.5 mmol) in CH2Cl2 10 mL at 40ꢀC. After the
o-hydroxy aryl ketone acylhydrazone was consumed (monitored
by TLC), the mixture was filtered to remove the resin, and washed
with 5 mL CH2Cl2, 6 mL H2O. The aqueous layer was extracted
with CH2Cl2 (3ꢁ5 mL). The combined extracts were washed with
sat. aq. NaHCO3 (3ꢁ5 mL), dried (MgSO4), filtered and concen-
trated in vacuo to give crude 1,2-diacylbenzene 4a. The pure prod-
uct 4a was isolated by column chromatography (Rf ¼ 0.6) on silica
gel (200–400 mesh) using EtOAc/hexanes (v/v ¼ 2/3) as eluent.
4a: White solid; mp 72–73ꢀC (lit12 72–73ꢀC); 1H-NMR (CCl4) d:
6.9–7.8 (m, 8H,), 2.3 (s, 6H); IR (KBr) n (cmꢁ1) 1684, 1612; MS: m/z 238
(Mþ 100) 223(23) 147(75) 119(31).
4b: White solid; mp 95–97ꢀC (lit12 95–97ꢀC); 1H-NMR (CCl4) d:
7.0–7.9 (m, 9H,), 3.8 (s, 6H); IR (KBr) n (cmꢁ1) 1680, 1604; MS: m/z 224
(Mþ 5) 209(100) 147(23) 119(31) 105(29).

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1,2-DIACYLBENZENES
2417
4c: White solid; mp 125–127ꢀC; H-NMR (CCl4) d: 7.2–8.4 (m, 8H),
4.5 (s, 3H); IR (KBr) n (cmꢁ1) 1690, 1605; MS: m/z 269 (Mþ 7) 254(100)
208(14) 180(16) 150(10) 147(29). Anal. Calcad for C15H11NO4: C 66.91
H 4.12 N 5.20 Found: C 66.60 H 4.07 N 5.38.
1
4d: White solid; mp 38–39ꢀC (lit8 39–40ꢀC); H-NMR (CCl4) d: 7.5
1
(s, 4H), 2.36 (s, 6H); IR (KBr) n (cmꢁ1) 1670, 1612; MS: m/z 162 (Mþ 4)
147(100) 91(37).
4e: White solid; mp 69–71ꢀC (lit12 oil); 1H-NMR (CCl4) d: 7.06–
7.78 (m, 8H,), 2.35 (s, 3H), 2.25 (s, 3H); IR (KBr) n (cmꢁ1) 1680, 1610;
MS: m/z 238 (Mþ 4) 223(100) 161(22) 105(20).
4f: White solid; mp 113–115ꢀC; H-NMR (CCl4) d: 7.15–8.5 (m, 7H),
1
2.45 (s, 6H); IR (KBr) n (cmꢁ1) 1690, 1620; MS: m/z 283 (Mþ 6) 268(100)
161(30) 119(36). Anal. Calcad for C16H13NO4: C 67.84 H 4.63 N 4.94
Found: C 67.68 H 4.67 N 4.88.
4g: White solid; mp 84–86ꢀC; H-NMR (CCl4) d: 7.0–7.7 (m, 7H),
1
2.3 (s, 3H), 2.4 (s, 3H); IR (KBr) n (cmꢁ1) 1687, 1620; MS: m/z 252 (Mþ 2)
237(100) 119(28) 105(6). Anal. Calcad for C17H16O2: C 80.93 H 6.39 Found:
C 81.50 H 6.39.
1
4h: oil; H-NMR (CCl4) d: 7.06–7.5 (m, 4H,), 2.3 (s, 9H); IR (film)
n (cmꢁ1) 1690, 1610; MS: m/z 176 (Mþ 2) 161(100) 105(25). Anal. Calcad
for C11H12O2: C 74.89 H 6.96 Found: C 74.53 H 6.89.
4i: White solid; mp 138–140ꢀC; 1H-NMR (CCl4) d: 7.13–7.65 (m, 7H,),
2.35 (s, 3H); IR (KBr) n (cmꢁ1) 1710, 1605; MS: m/z 292 (Mþ 22) 277(68)
215(54) 105(100). Anal. Calcad for C15H10O2Cl2: C 61.46 H 3.44 Found:
C 61.59 H 3.45.
4j: White solid; mp 141–142ꢀC; H-NMR (CCl4) d: 7.0–7.8 (m, 6H),
1
2.3 (s, 3H), 2.4 (s, 3H); IR (KBr) n (cmꢁ1) 1720, 1600; MS: m/z 306 (Mþ 6)
291(23) 215(11) 189(15) 119(100). Anal. Calcad for C16H12O2Cl2: C 62.56
H 3.94 Found: C 62.15 H 3.88.
4k: White solid; mp 70–72ꢀC; H-NMR (CCl4) d: 7.5–7.7 (m, 2H),
1
2.4 (s, 3H), 2.46 (s, 3H); IR (KBr) n (cmꢁ1) 1720, 1590; MS: m/z 230
(Mþ 1) 215(100). Anal. Calcad for C10H2O2Cl2: C 51.98 H 3.49 Found:
C 51.69 H 3.41.
4l: White solid; mp 40–41ꢀC (lit14 41–42ꢀC, lit12 39–41ꢀC); H-NMR
1
(CCl4) d: 10.05 (s, 1H), 6.74–7.7 (m, 4H,), 2.5 (s, 3H); IR (KBr) n (cmꢁ1
)
1670, 1612; MS: m/z 148 (Mþ 3) 147(15) 121(100) 105(27).
4m: White solid, mp 65–67ꢀC (lit7 64–67ꢀC); 1H-NMR (CC14) d:
9.93 (s, 1H), 7.27–7.87 (m, 9H,); IR (KBr) n (cmꢁ1) 1680, 1610; MS: m/z
210 (Mþ 100) 181(86) 133(7) 105(59).
Regeneration and Reuse of poly[styrene (iodoso diacetate)] from
recovered Poly(iodostyrene): Hydrogen peroxide (30%, 40 mL) was added
dropwise to acetic anhydride (145 mL) at 40ꢀC and was stirred for another

ORDER
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HUANG, ZHU, AND ZHANG
4 h. To this solution, 6.0 g of 2% cross-linked polyiodostyrene, which was
recovered by simply filtration after the reaction, was added and the solution
was kept at 40ꢀC for one day to give poly[styrene(iodoso diacetate)]. IR n
cmꢁ1 1654, 1500, 1410, 1360, 1280, 1000, 817, 760, 700. The functional
group is 1.97 mmol/g. It was applied to the reaction and has the same
activity as the first prepared poly[styrene(iodoso diacetate)].
ACKNOWLEDGMENT
The project 29932020 was supported by the National Natural
Foundation of China.
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Received in the USA November 6, 2000

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