One facile preparation of N-aroyl-N′-arylsulfonylhydrazines by oxidation of aromatic aldehyde N-arylsulfonylhydrazones with bis(trifluoroacetoxy)iodobenzene

Article abstract of DOI:10.1080/00397910600588538

N-aroyl-N′-arylsulfonylhydrazines can be obtained by oxidation of aromatic aldehyde N-arylsulfonylhydrazones with bis(trifluoroacetoxy)iodobenzene in acetone at room temperature in mild to good yields. Copyright Taylor & Francis Group, LLC.

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One Facile Preparation of
N‐Aroyl‐N′‐arylsulfonylhydrazines
by Oxidation of Aromatic Aldehyde
N‐Arylsulfonylhydrazones with
bis(Trifluoroacetoxy)iodobenzene
Zhenhua Shang a , John Reiner b & Kang Zhao b
a College of Chemical and Pharmaceutical Engineering , Hebei University of
Science and Technology , Shijiazhuang, China
b College of Pharmaceuticals and Biotechnology , Tianjin University ,
Tianjin, China
Published online: 21 Aug 2006.
To cite this article: Zhenhua Shang , John Reiner & Kang Zhao (2006) One Facile Preparation of
N‐Aroyl‐N′‐arylsulfonylhydrazines by Oxidation of Aromatic Aldehyde N‐Arylsulfonylhydrazones with
bis(Trifluoroacetoxy)iodobenzene, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 36:11, 1529-1535
To link to this article: http://dx.doi.org/10.1080/00397910600588538
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Synthetic Communicationsw, 36: 1529–1535, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600588538
One Facile Preparation of
N-Aroyl-N0-arylsulfonylhydrazines
by Oxidation of Aromatic
Aldehyde N-Arylsulfonylhydrazones
with bis(Trifluoroacetoxy)iodobenzene
Zhenhua Shang
College of Chemical and Pharmaceutical Engineering, Hebei University
of Science and Technology, Shijiazhuang, China
John Reiner and Kang Zhao
College of Pharmaceuticals and Biotechnology, Tianjin University,
Tianjin, China
Abstract: N-aroyl-N0-arylsulfonylhydrazines can be obtained by oxidation of aromatic
aldehyde N-arylsulfonylhydrazones with bis(trifluoroacetoxy)iodobenzene in acetone
at room temperature in mild to good yields.
Keywords: Aromatic aldehyde, N-aroyl-N0-arylsulfonylhydrazine, N-arylsulfonyl-
hydrazone, bis(trifloroacetoxy)iodobenzene, oxidation
INTRODUCTION
Many studies of the oxidation of aldehyde N-sulfonylhydrazones have been
reported. Bhati has described the oxidation of some arylidene-toluene-p-
sulfonylhydrazones by lead tetra-acetate to a-sulfonylhydraonobenzyl
acetates (2) as crystals.[1] In 1966, Butler comfirmed Bhati’s work, and
compounds (3) were obtained from compounds (2), which is believed to
Received in Japan November 16, 2005
Address correspondence to Zhenhua Shang, College of Chemical and Pharma-
ceutical Engineering, Hebei University of Science and Technology, Shijiazhuang,
050018, China. Tel.: 86-311-8863-2179; E-mail: zhenhuashang@yahoo.com.cn
1529

1530
Z. Shang, J. Reiner, and K. Zhao
Scheme 1.
occur when compounds 2 rapidly rearrange to compounds 3 through 1,4-acyl
migration (Scheme 1).[2] Furthermore, aldehyde sulfonylhydrazones can be
oxidized to their parent carbonyl compounds by Dess-Martin periodinane
(DMP),[3] H2O2/K2CO3,[4] thallium triaceatate,[5] N-bromosuccinimide
(NBS),[6] uranium hexafluoride,[7] and Br2.[8] Uiurg et al. found oxidation
of aromatic tosylhydrazones leads to benzoic acid when poly(bis-1,2-phenyle-
ne)diselenide was used as a catalyst.[9] In addition, intramolecular 1,3-dipolar
cycloadducts through nitrilesulfonimides, oxidized from aldehyde sulfonylhy-
drazones, react with dipolarophile.[10] Herein, we report that aromatic
aldehyde N-sulfonylhydrazones (1) react smoothly with the organic
iodine(III) reagent, bis(trifloroacetoxy)iodobenzene (BTI), at room tempera-
ture to efficiently afford N-acyl-N0-sulfonylhydrazines (4) in mild to good
yields (Scheme 2).
RESULTS AND DISCUSSION
Commercially available BTI is commonly used as an efficient oxidizing
reagent in organic synthesis. Many applications of BTI have been
reported,[11–16] a reflection both of its mild reactivity along with a low
by-product profile. In the current report, similar advantages of this
reagent, mild reactivity and cleanly prepared products, were observed
(Table 1).
Oxidation of the aromatic aldehyde N-arylsulfonylhydrazones implicated
that all the reactions proceeded rapidly and finished within 10 min. The
oxidative yield was lower than others when the starting material contained a
furan ring, whereas other functional groups had little influence.
The infrared spectrum showed some principal features of the product
4a, strong bands at 3343 cm21 and 3256 cm21, which may be assigned
Scheme 2.

N-Aroyl-N0-arylsulfonylhydrazines
1531
Table 1. Conversion of aromatic aldehyde arylsulfonylhydrazones into N-aroyl-N0-
arylsulfonylhydrazines
Reaction time
(min)
Isolated yield
(%)
Entry
4a
Ar
Ar0
3
3
3
3
3
83
88
77
80
84
4b
4c
4d
4e
4f
2
2
2
7
76
65
45
82
4g
4h
4i
to –NH-; a carbonyl stretching band at 1681 cm21 and a sulfonyl stretching
band at 1328 cm21 and 1166 cm21. In addition, the proton NMR showed
two protons in the low field at 8.52 ppm and 9.92 ppm. All the data
suggested the product 4a may be N-(4-methylbenzenesulfonyl)-N0-
(4-methyl-benzoyl)hydrazine. N-(4-methylbenzenesulfonyl)-N0-(4-methyl-
benzoyl)hydrazine, prepared from p-methylbenzenesulfonyl chloride
reacting with benzenesulfonyl chloride,[17] showed the same physical and
chemical properties with 4a.
A proposal for the reaction mechanism is shown in Scheme 3. The
hydrazone 1 can be oxidized to nitronium ion II, which reacts with trifluoro-
acetic acid anion and eliminates iodobenzene and trifluoroacetic acid to
afford IV. The intermediate V comes from IV through 1,4-acyl migration
and is attacked by trifluoroacetic acid anion to eliminate trifluoroacetic
anhydride and form product 4.

1532
Z. Shang, J. Reiner, and K. Zhao
Scheme 3.
CONCLUSION
The present method provides a rapid and productive synthesis of N-aroyl-N0-
arylsulfonylhydrazines. This method is particularly advantageous, involving
the use of easily handled BTI as a mild reaction reagent, which produced
the desired products in good yields and a short period of time.
EXPERIMENTAL
Melting points were determined on a X-4 micro hot stage and are uncorrected.
1
IR spectra were recorded on FTS 3000 instrument (BIO-RAD). H NMR
spectra were recorded on Bruker AV 400-MHz instrument using acetone-d6
as a solvent, and chemical shifts (d) are in ppm relative to TMS. All
solvents were dried.
General Procedure
A dried round-bottomed flask was charged with aldehyde N-sulfonylhydra-
zones (1 mmol),[18] bis(trifluoroacetoxy) iodobenzene (BTI, 1.2 mmol), and
anhydrous acetone (5 mL). This mixture was stirred at room temperature
and monitored by TLC. When the reaction was complete, purification of the
product directly by flash chromatography (silica gel, ethyl acetate–
petroleum ether) three times afforded the products as solids.
Data
4a: N-(4-methylbenzenesulfonyl)-N0-(4-methyl-benzoyl)hydrazine mp:
201–2028C; IR (KBr): 3343, 3256, 1681, 1328, 1166cm21; 1H NMR: d ppm

N-Aroyl-N0-arylsulfonylhydrazines
1533
2.35 (s, 6H), 7.23–7.25 (d, 2H, J ¼ 8.0 Hz), 7.29–7.31 (d, 2H, J ¼ 8.0 Hz),
7.66–7.68 (d, 2H, J ¼ 8.4 Hz), 7.78–8.00 (d, 2H, J ¼ 8.0 Hz), 8.52 (s, 1H),
9.92 (s, 1H).
4b: N-benzenesulfonyl-N0-benzoylhydrazine mp: 1938C (lit.[19] 1708C); IR
(KBr): 3311, 3139, 1670, 1341, 1170 cm21 1H NMR: d ppm 7.41–7.46
;
(m, 2H), 7.48–7.52 (m, 3H), 7.58–7.63 (m, 1H), 7.75–7.78 (m, 2H), 7.92–
7.95 (m, 2H), 8.67 (s, 1H), 10.01 (s, 1H).
4c: N-benzenesulfonyl-N0-(4-methyl-benzoyl)hydrazine mp: 156–1578C;
IR (KBr): 3342, 3127, 1663, 1341, 1169 cm21 1H NMR: d ppm 2.34
;
(s, 3H), 7.23–7.25 (d, 2H, J ¼ 8.0 Hz), 7.47–7.51 (m, 2H), 7.57–7.62
(m, 1H), 7.65–7.67 (d, 2H, J ¼ 8.4 Hz), 7.91–7.93 (m, 2H), 8.65 (s, 1H),
9.98 (s, 1H).
4d: N-benzenesulfonyl-N0-(4-bromo-benzoyl)hydrazine mp: 202–2048C
(lit.[19] 200–2028C); IR (KBr): 3338, 3147, 1681, 1320, 1173 cm21 1H
;
NMR: d ppm 7.49–7.53 (m, 2H), 7.59–7.64 (m, 3H), 7.68–7.70 (d, 2H,
J ¼ 8.4 Hz), 7.91–7.93 (m, 2H), 8.65 (s, 1H), 10.05 (s, 1H).
4e: N-benzenesulfonyl-N0-(4-methoxy-benzoyl)hydrazine mp: 179–1818C
(lit.[19] 189–1908C); IR (KBr): 3240, 3100, 1650, 1330, 1160 cm21 1H
;
NMR d: ppm 3.84 (s, 3H), 6.94–6.97 (m, 2H), 7.47–7.51 (m, 2H), 7.58–
7.60 (m, 1H), 7.74–7.76 (d, 2H, J ¼ 8.8 Hz), 7.90–7.92 (d, 2H,
J ¼ 6.8 Hz), 8.59 (s, 1H), 9.88 (s, 1H).
4f: N-benzoyl-N0-(4-chloro-benzenesulfonyl)hydrazine mp: 1948C; IR
1
(KBr): 3253, 1652, 1349, 1164 cm21; H NMR: d ppm 7.43–7.47 (m, 2H),
7.53–7.56 (m, 3H), 7.76–7.78 (m, 2H), 7.91–7.94 (m, 2H), 8.01 (s, 1H),
10.03 (s, 1H).
4g: N-(4-methylbenzoyl)-N0-(4-chloro-benzenesulfonyl)hydrazine mp:
1
210–2128C; IR (KBr): 3254, 1651, 1346, 1164 cm21; H NMR: d ppm 2.47
(s, 3H), 7.35–7.37 (d, 2H, J ¼ 8.0 Hz), 7.59–7.62 (m, 2H), 7.64–7.69
(m, 2H), 7.96–7.98 (dd, 2H, J ¼ 2.0 Hz, J ¼ 2.8 Hz), 8.07 (s, 1H).
4h: N0-4-chlorobenzenesulfonylfurane-2-carbohydrazide mp: 198–2008C;
1
IR (KBr): 3292, 3140, 1660, 1349, 1167 cm21; H NMR: d ppm 6.64–6.66
(dd, 1H, J ¼ 1.6 Hz, J ¼ 3.6 Hz), 7.14–7.15 (d, 1H, J ¼ 3.6 Hz), 7.62–7.65
(m, 2H), 7.70–7.73 (m, 1H), 7.93–7.97 (m, 2H), 8.28 (s, 1H), 9.24 (s, 1H).
4i: N-(4-bronobenzoyl)-N0-(4-chlorobenzenesulfonyl)hydrazine mp: 209–
1
2108C; IR (KBr): 3329, 3146, 1641, 1380, 1175 cm21; H NMR: d ppm
7.55–7.58 (m, 2H), 7.63–7.66 (m, 2H), 7.70–7.72 (m, 2H), 7.91–7.94
(m, 2H), 8.86 (s, 1H), 10.12 (s, 1H).

1534
Z. Shang, J. Reiner, and K. Zhao
ACKNOWLEDGMENTS
We acknowledge the Outstanding Young Scholarship from National Science
Foundation of China (NSFC) (No. 30125043), the Basic Research Project
(No. 2002CCA01500) of the Ministry of Science and Technology (MOST),
and the Cheung Kong Scholars Programme for the financial support.
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