Nitro-group-directed selective deacylation and desulfonation

Article abstract of DOI:10.1055/s-2006-942451

Nitro-substituted phenolic esters and sulfonates were successfully and selectively deacylated and desulfonated, respectively. The directing effect of the nitro group is supported by the excellent regioselectivities and good yields. These reactions demonst

Full text of DOI:10.1055/s-2006-942451

2478
PAPER
Nitro-Group-Directed Selective Deacylation and Desulfonation
N
itro-Group-Direc
i
tedSel
u
ective
D
eacy
j
lation
i
and
D
e
e
sulfonation Ji, Chunbao Li*
Department of Chemistry, Tianjin University, Tianjin 300072, P. R. of China
Fax +86(22)27403475; E-mail: lichunbao@tju.edu.cn
Received 14 February 2006; revised 15 March 2006
OAc
OH
Abstract: Nitro-substituted phenolic esters and sulfonates were
successfully and selectively deacylated and desulfonated, respec-
tively. The directing effect of the nitro group is supported by the ex-
NO2
NO2
AlCl3, CHCl3
r.t., 1 h
cellent regioselectivities and good yields. These reactions
demonstrate for the first time that the complexation of AlCl3 with
the phenolic nitro group is stronger than that with the phenolic ester
OAc
OAc
1a
2a
or sulfonate group alone. The mechanism for the selective deacyla-
tion and desulfonation directed by the nitro group is proposed.
OAc
OH
H
C
NAr
NHAc
Key words: selective deacylation, selective desulfonation, nitro
group, AlCl3, complexation
OAc
OAc
I
II
It is well documented that phenolic esters undergo Fries
rearrangement to produce o- and p- acylphenols.1–4 This is
Scheme 1 Selective deacetylation on substrates 1a, I and II
the most commonly used method for preparing hydroxy
aromatic ketones. The catalyst used in this reaction is usu- Similarly, a series of substrates 1 and 3 (Schemes 2 and 3)
ally AlCl3, a Lewis acid. It is known that Lewis acids are were all selectively deacylated or desulfonated in high
capable of coordinating to atoms bearing a lone pair or a yields and at high reaction rates except for the failure of
partial negative charge such as in amino, imino and nitro the selective demesylation of 1i (Scheme 2). Thus a series
groups,5 which are Lewis bases. For phenolic esters bear- of nitro-substituted phenolic esters and sulfonates 2 and 4
ing these groups, a different complexation from that re- (Schemes 2 and 3) was synthesized and these compounds
quired for the Fries reaction could be speculated to are shown in Tables 1 and 2. In all cases, the regioselec-
predominate, and different products other than the hy- tivity is excellent and we did not detect any regioisomers.
droxy aromatic ketones from the Fries rearrangement All the products were characterized spectroscopically.
1
would be expected. We believe that a nitro group could di- The IR (3220–3430 cm–1) and H NMR (10.45–10.76
rect a selective deacylation or desulfonation in phenolic ppm) spectra display typical intramolecular hydrogen
esters, although Fries rearrangement of esters of 2-nitro- bonding.
resorcinol leading to the normal product, e.g. hydroxyl ar-
On replacing AlCl3 with other Lewis acid such as BF3,
omatic ketone in moderate yields has been reported.3,4
ZrCl4, and FeCl3, we found that the reaction rates were
However we believe that AlCl3 should coordinate more
tremendously decreased. To further demonstrate the
strongly to the oxygen atoms in the nitro group and in the
neighboring nitro group effect, we prepared o-nitrophenyl
acetate, m-nitrophenyl acetate and p-nitrophenyl acetate.
The three acetates were similarly treated with AlCl3 at
room temperature for 24 hours. Only o-nitrophenyl ace-
tate afforded the desired product, o-nitrophenol, in 85%
yield. In contrast, the other two acetates did not react at
neighboring ester group than it does to an isolated phenol-
ic ester. This type of complexation would lead to selective
deacylation and desulfonation, which have not previously
been investigated. This work studies these reactions and
proposes a mechanism for them.
We started by subjecting 1a, I, II (Scheme 1) to the action all. When an alkyl nitro acetate, 1-nitro-2-butyl acetate,
of AlCl3. At temperatures from 0 °C to 60 °C in anhydrous was treated with AlCl3, the reaction was very sluggish.
chloroform, no reactions took place for I and II. We were The starting materials remained practically unchanged af-
delighted to find that 1a was selectively deacylated into ter two days with small amount of side-products and no
2a when 1a was treated with AlCl3 (1.0 equiv) at 20 °C desired deacylation products were detected.
(Scheme 1).
The substrates 1a–f, 3a–e (Schemes 2 and 3) were pre-
pared by the diacylation of 2-nitrohydroquinone and 4-ni-
troresorcinol using the corresponding acyl chloride and
anhydrous triethylamine in anhydrous chloroform.3,4 Sim-
ilarly, the substrates 1g–i, 3f and 3g (Schemes 2 and 3)
were prepared by the disulfonation of 2-nitrohydroqui-
SYNTHESIS 2006, No. 15, pp 2478–2482
Advanced online publication: 28.06.2006
x
x.
x
x
.
2
0
0
6
none and 4-nitroresorcinol using the corresponding sulfo-
DOI: 10.1055/s-2006-942451; Art ID: F02206SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Nitro-Group-Directed Selective Deacylation and Desulfonation
2479
OR
NO2
OH
NO2
NO2
OR
NO2
OH
AlCl3
AlCl3
CHCl3
CHCl3
OR
OR
OR
OR
1
2
3
4
3a, 4a: R = MeCO
3b, 4b: R = EtCO
3c, 4c: R = Me(CH2)16CO
3d, 4d: R = PhCO
3e, 4e: R = o-Cl-C6H4CO
3f, 4f: R = PhSO2
3g, 4g: R = Ts
1a, 2a: R = MeCO
1b, 2b: R = EtCO
1c, 2c: R = Me(CH2)3CO
1d, 2d: R = Me(CH2)16CO
1e, 2e: R = PhCO
1f, 2f: R = o-Cl-C6H4CO
1g, 2g: R = PhSO2
1h, 2h: R = Ts 1i: R = Ms
Scheme 3 Selective deacylation and desulfonation of 3
Scheme 2 Selective deacylation and desulfonation of 1
atures and longer reaction times are needed. This can be
attributed to the stabilization of the carbonyl cation by the
electron-donating alkyl groups. RCO+ AlCl4– is less elec-
trophilic towards the phenolic hydroxy group than ArCO+
nyl chloride and anhydrous triethylamine in anhydrous
chloroform.3,4
By comparing the reaction rates of the deacylation and
desulfonation, a general mechanism represented by de-
sulfonation can be proposed (Scheme 4). In most cases,
the selective reaction of aliphatic esters needed 1.0–2.0
equivalents of AlCl3, and took less than ten hours at room
temperature for completion. Except for aromatic carboxy-
lic esters and aromatic sulfonates, higher reaction temper-
–
AlCl4 . This in turn reduces the esterification reaction (the
reverse reaction). For desulfonation (Scheme 4), the lim-
iting step is the formation of sulfonic chloride via the at-
tack of the chloride ion on the sulfur. The more positively
charged the sulfur, the faster the desulfonation. Therefore
Table 1 Selective Deacylation of 1a–f and Selective Desulfonation of 1g–i Using AlCl3
Entry
Product
2a
AlCl3 (equiv)
Temp (°C)
Time (h)
Yield (%)a
mp (°C)
1
2
3
4
5
6
7
8
9
1.0
1.5
1.5
2.0
2.0
2.0
2.0
2.0
2.0
20
20
20
20
20
20
20
20
60
1
1.5
2.5
3.5
17
3
85
91
80
92
81
83
91
88
NR
80–81 (846)
58–60
2b
2c
36–38
2d
60–62
2e
95–97 (95.5–97.57)
132–134
69–71
2f
2g
7
2h
12
24
107–109
2i
a Yield of isolated product.
Table 2 Selective Deacylation of 3a–e and Selective Desulfonation of 3f and 3g Using AlCl3
Entry
Product
4a
AlCl3 (equiv)
Temp (°C)
Time (h)
Yield (%)a
mp (°C)
86–88
1
2
3
4
5
6
7
1.0
1.5
2.0
2.0
2.0
2.0
2.0
20
20
20
20
20
60
20
1
3
73
81
82
85
71
77
77
4b
63–65
4c
3.5
10
3
56–58
4d
121–123 (1248)
114–116
78–80
4e
4f
1.5
6
4g
87–89
a Yield of isolated product.
Synthesis 2006, No. 15, 2478–2482 © Thieme Stuttgart · New York

2480
X. Ji, C. Li
PAPER
we observed benzenesulfonate was desulfonated much better ability to complex with AlCl3 than an isolated phe-
faster than tosylate (Table 1, entries 7, 8 and Table 2, en- nolic ester group does (Fries rearrangement). The regiose-
tries 5, 6). In mesylate, the electron-donating methyl lectivity is excellent and the reaction rates and yields are
group makes the sulfur less positively charged than in ar- high. The products are useful intermediates in organic
ylsulfonate. We could not detect any trace amount of de- synthesis. The products from the selective desulfonation
mesylation product when substrate 1i was treated with represent a new type of compounds.
AlCl3 at 60 °C for 24 hours (Table 1, entry 9).
All moisture-sensitive reactions were performed in flame-dried
Cl
O
Cl
O
glassware. Triethylamine and chloroform were dried over NaOH
and P2O5, respectively and distilled prior to use. AlCl3 were sub-
limed prior to use. Other reagents were purified by standard labora-
tory procedure. All organic extracts were dried over Na2SO4. The
boiling point range of PE used in flash chromatography and crystal-
lization was 60–90 °C. The products were purified by crystalliza-
tion or flash column chromatography. Silica gel 60 (200–300 mesh)
and silica gel 60 F254 were used for column chromatography and
analytical TLC, respectively. Melting points were determined on a
Reichert hot-stage apparatus and are uncorrected. IR spectra were
determined on a Bio-Rad FTS3000 spectrometer. NMR spectra
were recorded on Bruker AC 400 or Varian INOVA500 spectro-
meters. Mass spectral data (ESI–MS) were obtained from Finnigan
LCQ Advatage MAX spectrometer. Microanalyses were performed
with Vanio-EL Analysensysteme Gmbl analyzer.
O
S
O
S
Al
Cl–
Ar
Ar
O
Ar
Ar
+
O
NO2
O
N
AlCl3
O
O
S
O
S
O
O
O
O
Cl
Cl
O
ArSO2Cl
Al
O
N
OH
AlCl3
NO2
O
S
aq HCl
Ar
–
O
Ar
AlCl4
–
AlCl4
O
O
S
O
S
O
Ar
O
O
O
Scheme 4 Proposed mechanism represented by selective desulfona-
tion using AlCl3
Selective Deacylation and Desulfonation; Typical Procedure
The substrate 1 or 3 (1 mmol) was dissolved in anhyd CHCl3 (30
mL) and cooled to 0 °C. After AlCl3 (1.0–2.0 equiv) was added in
portions within 0.5 h, the reaction was allowed to warm to r.t. or re-
fluxed (as indicated in the Tables 1 and 2). Upon addition of AlCl3
the reaction solution became red. The reaction was monitored via
TLC. When the substrate disappeared, the reaction was cooled to
r.t., and reaction mixture was treated with 10% aq HCl, extracted
with CH2Cl2 (3 × 50 mL), dried with Na2SO4 and concentrated. The
residue was purified by crystallization or flash column chromatog-
raphy.
Most of the deacylated compounds are useful intermedi-
ates.6–15 For example, 4-hydroxy-3-nitrophenyl acetate
(2a) was used in synthesizing bioactive compounds9 such
as calcium ion indicators.12 4-Hydroxy-3-nitrophenyl
benzoate (2e) is a useful intermediate for a new material
with a higher concentration of nonlinear optics chro-
mophores.10 Acetate 2a has been made by refluxing sub-
strate 1,4-diacetoxybenzene 1a for four hours with ceric
ammonium nitrate (CAN) in methanol in 40% yield.16 It
has also been produced as a by-product when 1a was treat-
ed with fuming nitric acid at 5–8 °C6 or with peroxynitrite,
FeCl3 and ethylenediaminetetraacetic acid (EDTA) in
4-Hydroxy-3-nitrophenyl Propionate (2b)
Yield: 91%; yellow needles; mp 58–60 °C. The product was puri-
fied by flash column chromatography using PE–EtOAc (15:1) and
crystallization with PE.
aqueous phosphate buffer.13 3-Hydroxy-4-nitrophenyl IR (KBr): 3386, 3089, 2947, 2925, 1765, 1549, 1244, 1138, 940,
benzoate (4d) has been obtained in 33% yield when 3-
benzoxyphenol was treated with nitric acid in glacial ace-
tic acid17 or in 38% yield with concentrated nitric acid in
acetic acid.8
794 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.28 (t, J = 7.6 Hz, 3 H), 2.61 (q,
J = 7.6 Hz, 2 H), 7.17 (d, J = 9.2 Hz, 1 H), 7.35 (dd, J = 2.8, 9.2 Hz,
1 H), 7.87 (d, J = 2.8 Hz, 1 H), 10.50 (s, 1 H).
13C NMR (125 MHz, CDCl3): d = 9.10, 27.76, 117.69, 120.81,
131.84, 133.84, 143.16, 153.00, 172.78.
Selective desulfonation of polyphenolic sulfonates has
never been realized before. This represents the first selec-
tive desulfonation procedure of polyphenolic sulfonates.
ESI–MS: m/z = 211 [M+ + 1].
The products of the selective desulfonation are new types Anal. Calcd for C9H9NO5: C, 51.19; H, 4.30; N, 6.63. Found: C,
51.27; H, 4.45; N, 6.53.
of compounds. The hydroxyl group is electron-donating,
especially under basic conditions. We speculate that this
would dramatically influence the behavior of the aryl car-
bon and the sulfonoxy oxygen bond and find applications
4-Hydroxy-3-nitrophenyl Valerate (2c)
Yield: 80%; yellow needles, mp 36–38 °C. The product was puri-
fied by flash column chromatography using PE–Et2O (3:1) and
in organic synthesis. One of the possible applications is in
the modified Suzuki reaction,18–21 where the reaction rate
would be dramatically improved due to the electron-do-
nating effect of the hydroxyl group. We have started this
investigation.
crystallization with PE.
IR (KBr): 3269, 3098, 2960, 2935, 1765, 1539, 1239, 1137, 1099,
944, 843 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.00 (t, J = 7.0 Hz, 3 H), 1.45–1.49
(m, 2 H), 1.75–1.78 (m, 2 H), 2.59 (t, J = 7.5 Hz, 2 H), 7.20 (d, J =
9.5 Hz, 1 H), 7.36 (dd, J = 2.0, 9.0 Hz, 1 H), 7.88 (d, J = 3.5 Hz, 1
H), 10.50 (s, 1 H).
In conclusion, we have established a new procedure for
the selective deacylation and desulfonation of polyphe-
nolic esters directed by a nitro group. These reactions
demonstrate that a nitro group on a phenolic ester has a
13C NMR (125 MHz, CDCl3): d = 13.82, 22.41, 27.06, 34.06,
117.68, 120.80, 129.06, 131.87, 143.15, 153.00, 172.12.
Synthesis 2006, No. 15, 2478–2482 © Thieme Stuttgart · New York

PAPER
Nitro-Group-Directed Selective Deacylation and Desulfonation
2481
ESI–MS: m/z = 239 [M+ + 1].
ESI–MS: m/z = 309 [M+ + 1].
Anal. Calcd for C11H13NO5: C, 55.23; H, 5.48; N, 5.85. Found: C,
55.34; H, 5.63; N, 5.75.
Anal. Calcd for C13H11SO6N: C, 50.48; H, 3.58; N, 4.53. Found: C,
50.50; H, 3.59; N, 4.50.
4-Hydroxy-3-nitrophenyl Stearate (2d)
Yield: 92%; yellow needles; mp 60–62 °C. The product was puri-
fied by crystallizing with EtOH.
3-Hydroxy-4-nitrophenyl Acetate (4a)
Yield: 73%; yellow needles; mp 86–88 °C. The product was puri-
fied by flash column chromatography using PE–Et2O (4:1) and
crystallization with PE.
IR (KBr): 3293, 3094, 2955, 2918, 1749, 1545, 1245, 1219, 1154,
951, 828 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.88 (t, J = 7.2 Hz, 3 H), 1.26–1.41
(m, 28 H), 1.75 (t, J = 7.6 Hz, 2 H), 2.56 (t, J = 7.6 Hz, 2 H), 7.16
(d, J = 8.8 Hz, 1 H), 7.34 (dd, J = 2.8, 9.2 Hz, 1 H), 7.86 (d, J = 2.8
Hz, 1 H), 10.45 (s, 1 H).
IR (KBr): 3253, 3083, 2946, 1758, 1530, 1204, 1138, 978, 847
cm–1.
1H NMR (500 MHz, CDCl3): d = 2.34 (s, 3 H), 6.79 (dd, J = 2.5, 7.0
Hz, 1 H), 6.95 (d, J = 2.5 Hz, 1 H), 8.14 (d, J = 6.5 Hz, 1 H), 10.71
(s, 1 H).
13C NMR (125 MHz, CDCl3): d = 14.25, 22.87, 25.02, 29.29, 29.41,
29.51, 29.54, 29.63, 29.68, 29.78, 29.81, 29.83, 29.85, 29.86, 29.89,
32.13, 34.37, 110.00, 117.69, 120.80, 131.86, 143.16, 153.00,
172.14.
13C NMR (125 MHz, CDCl3): d = 21.77, 113.04, 115.03, 127.11,
131.89, 157.00, 158.03, 168.65.
ESI–MS: m/z = 197 [M+ + 1].
Anal. Calcd for C8H7NO5: C, 48.74; H, 3.58; N, 7.10. Found: C,
48.80; H, 3.61; N, 7.08.
ESI–MS: m/z = 421 [M+ + 1].
Anal. Calcd for C24H39NO5: C, 68.38; H, 9.32; N, 3.32. Found: C,
68.42; H, 9.41; N, 3.13.
3-Hydroxy-4-nitrophenyl Propionate (4b)
Yield: 81%; yellow needles; mp 63–65 °C. The product was puri-
fied by flash column chromatography using PE–Et2O (4:1) and
crystallization with PE.
4-Hydroxy-3-nitrophenyl 2-Chlorobenzoate (2f)
Yield: 83%; yellow needles; mp 132–134 °C. The product was pu-
rified by crystallizing with EtOH.
IR (KBr): 3228, 3095, 1742, 1536, 1256, 1101, 1038, 894 cm–1.
IR (KBr): 3205, 2986, 2945, 1763, 1540, 1264, 1126, 1071, 970,
846 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.27 (d, J = 9.5 Hz, 1 H), 7.43–
7.45 (m, 1 H), 7.53–7.56 (m, 3 H), 8.05 (d, J = 3.0 Hz, 1 H), 8.06
(d, J = 7.5 Hz, 1 H), 10.55 (s, 1 H).
1H NMR (500 MHz, CDCl3): d = 1.27 (t, J = 7.5 Hz, 3 H), 2.63 (q,
J = 7.5 Hz, 2 H), 6.77 (dd, J = 2.5, 9.0 Hz, 1 H), 6.95 (d, J = 2.5 Hz,
1 H), 8.14 (d, J = 9.5 Hz, 1 H), 10.72 (s, 1 H).
13C NMR (125 MHz, CDCl3): d = 117.86, 121.02, 127.07, 128.72,
131.75, 131.83, 132.20, 133.42, 133.84, 134.89, 143.01, 153.30,
163.89.
13C NMR (125 MHz, CDCl3): d = 8.83, 27.77, 112.36, 114.41,
126.47, 131.19, 156.41, 157.58, 171.62.
ESI–MS: m/z = 211 [M+ + 1].
ESI–MS: m/z 293 [M+ + 1].
Anal. Calcd for C9H9NO5: C, 51.19; H, 4.30; N, 6.63. Found: C,
51.25; H, 4.44; N, 6.60.
Anal. Calcd for C13H8NO5Cl: C, 53.17; H, 2.75; N, 4.77. Found: C,
53.18; H, 2.70; N, 4.72.
3-Hydroxy-4-nitrophenyl Stearate (4c)
Yield: 82%; yellow needles; mp 56–58 °C. The product was puri-
4-Hydroxy-3-nitrophenyl Benzenesulfonate (2g)
Yield: 91%; yellow needles; mp 69–71 °C. The product was puri-
fied by flash column chromatography using PE–Et2O (3:1) and
crystallization with a mixture of EtOAc and PE.
IR (KBr): 3310, 3089, 1625, 1532, 1243, 1188, 944, 839 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.13 (d, J = 9.0 Hz, 1 H), 7.30 (dd,
J = 3.0, 9.0 Hz, 1 H), 7.57–7.62 (m, 2 H), 7.70 (d, J = 3.0 Hz, 1 H),
7.73–7.76 (m, 1 H), 7.88 (d, J = 8.5 Hz, 2 H), 10.51 (s, 1 H).
fied by crystallizing with PE.
IR (KBr): 3213, 3119, 2955, 2921, 1765, 1544, 1262, 1141, 973,
845 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.88 (t, J = 5.6 Hz, 3 H), 1.26–1.42
(m, 28 H), 1.71–1.81 (m, 2 H), 2.58 (t, J = 7.5 Hz, 2 H), 6.77 (dd,
J = 2.5, 9.5 Hz, 1 H), 6.94 (d, J = 2.5 Hz, 1 H), 8.14 (d, J = 9.0 Hz,
1 H), 10.72 (s, 1 H).
13C NMR (125 MHz, CDCl3): d = 117.82, 121.35, 128.00, 128.74,
13C NMR (125 MHz, CDCl3): d = 14.82, 23.38, 25.38, 29.70, 29.74,
29.89, 30.05, 30.11, 30.27, 30.32, 30.35, 30.36, 30.37, 30.39, 32.61,
34.84, 35.04, 113.06, 115.11, 115.96, 127.14, 157.10, 158.27,
171.64.
129.41, 129.69, 132.34, 135.01, 135.07, 141.63.
ESI–MS: m/z = 295 [M+ + 1].
Anal. Calcd for C12H9SO6N: C, 48.81; H, 3.07; N, 4.74. Found: C,
48.83; H, 3.15; N, 4.73.
ESI–MS: m/z = 421 [M+ + 1].
Anal. Calcd for C24H39NO5: C, 68.38; H, 9.32; N, 3.32. Found: C,
68.45; H, 9.30; N, 3.29.
4-Hydroxy-3-nitrophenyl 4-Toluenesulfonate (2h)
Yield: 88%; yellow needles; mp 107–109 °C. The product was pu-
rified by crystallizing with a mixture of EtOAc and PE.
3-Hydroxy-4-nitrophenyl 2-Chlorobenzoate (4e)
Yield: 71%; yellow needles; mp 114–116 °C. The product was pu-
rified by crystallizing with a mixture of EtOAc and PE.
IR (KBr): 3380, 3099, 1539, 1243, 1176, 831 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.47 (s, 3 H), 7.11 (d, J = 9.2 Hz,
1 H), 7.29 (dd, J = 2.8, 9.2 Hz, 1 H), 7.36 (d, J = 8.4 Hz, 2 H), 7.68
(d, J = 8.4 Hz, 1 H), 7.73 (dd, J = 1.6, 8.4 Hz, 2 H), 10.48 (s, 1 H).
13C NMR (125 MHz, CDCl3): d = 21.92, 118.83, 121.27, 128.78,
130.28, 132.06, 132.43, 133.20, 141.75, 146.34, 153.90.
IR (KBr): 3203, 3118, 1753, 1533, 1234, 1143, 1034, 970, 844
cm–1.
1H NMR (500 MHz, CDCl3): d = 6.95 (dd, J = 2.5, 9.0 Hz, 1 H),
7.12 (d, J = 2.5 Hz, 1 H), 7.41–7.44 (m, 1 H), 7.53–7.57 (m, 2 H),
8.05 (d, J = 7.5 Hz, 1 H), 8.21 (d, J = 9.5 Hz, 1 H), 10.76 (s, 1 H).
Synthesis 2006, No. 15, 2478–2482 © Thieme Stuttgart · New York

2482
X. Ji, C. Li
PAPER
13C NMR (125 MHz, CDCl3): d = 112.59, 114.44, 126.62, 126.92,
127.98, 131.47, 131.62, 132.15, 133.93, 134.82, 156.46, 157.30,
162.55.
References
(1) Trost, B. M.; Fleming, L. Comprehensive Organic
Synthesis, Vol. 2; Oxford: England, 1991, 745.
(2) Barton, D.; Stoddart, J. F.; Ollis, W. D. Comprehensive
Organic Chemistry, Vol. 1; Oxford: England, 1979, 1170.
(3) Amin, G. C.; Chaughuley, A. S. U. J. Indian Chem. Soc.
1959, 36, 617.
ESI–MS: m/z = 293 [M+ + 1].
Anal. Calcd for C13H8NO5Cl: C, 53.17; H, 2.75; N, 4.77. Found: C,
53.28; H, 2.69; N, 4.70.
(4) Amin, G. C.; Chaughuley, A. S. U. J. Indian Chem. Soc.
1959, 36, 833.
(5) Ono, N. The Nitro Group in Organic Synthesis; John Wiley:
3-Hydroxy-4-nitrophenyl Benzenesulfonate (4f)
Yield: 77%; yellow needles; mp 78–80 °C. The product was puri-
fied by flash column chromatography using PE–Et2O (3:1) and
crystallization with a mixture of Et2O and PE.
New York, 2001, 274.
(6) Kehrmann, F.; Klopfenstein, W. Helv. Chim. Acta 1923, 6,
952.
IR (KBr): 3260, 3096, 1621, 1535, 1265, 1194, 973, 876 cm–1.
1H NMR (500 MHz, CDCl3): d = 6.71 (dd, J = 9.5 Hz, 1 H), 6.84 (d,
J = 2.5 Hz, 1 H), 7.59 (t, J = 8.0 Hz, 2 H), 7.74 (t, J = 8.0 Hz, 1 H),
7.89 (d, J = 7.5 Hz, 2 H), 8.08 (d, J = 9.5 Hz, 1 H), 10.64 (s, 1 H).
13C NMR (125 MHz, CDCl3): d = 113.11, 114.54, 126.85, 128.41,
129.54, 132.16, 134.88, 134.94, 155.58, 156.19.
(7) Keller, P. Bull. Soc. Chim. Fr. 1994, 131, 27.
(8) Shridhar, D. R.; Bhagat, R.; Reddy, G. Indian J. Chem., Sect.
B: Org. Chem. Incl. Med. Chem. 1986, 25, 883.
(9) Sommer, H. Z.; Krenzer, J. US Patent, 3919289, 1975;
Chem. Abstr. 1975, 84, 58995d.
(10) Trollsas, M.; Orrenius, C.; Sahlen, F.; Gedde, U. W.; Norin,
T.; Hult, A.; Hermann, D.; Rudquist, P.; Komitov, L.;
Lagerwall, S. T.; Lindstrom, J. J. Am. Chem. Soc. 1996, 118,
8542.
ESI–MS: m/z = 295 [M+ + 1].
Anal. Calcd for C12H9SO6N: C, 48.81; H, 3.07; N, 4.74. Found: C,
48.90; H, 3.14; N, 4.70.
(11) Svensson, M.; Helgee, B.; Skarp, K.; Andersson, G. J.
Mater. Chem. 1998, 8, 353.
(12) Smith, G. A.; Metcalfe, J. C.; Clarke, S. D. J. Chem. Soc.,
Perkin Trans. 2 1993, 1195.
3-Hydroxy-4-nitrophenyl 4-Toluenesulfonate (4g)
Yield: 77%; yellow needles; mp 87–89 °C. The product was puri-
fied by crystallizing with EtOH.
(13) Claus, J.; Gavin, A. E.; Takahiro, K.; Lars, E.; Helmut, S.
Chem. Res. Toxicol. 2000, 13, 3.
(14) Atkinson, P. J.; Bromidge, S. M.; Duxon, M. S.; Gaster, L.
M.; Hadley, M. S.; Hammond, B.; Johnson, C. N.;
Middlemiss, D. N.; North, S. E.; Price, G. W.; Rami, H. K.
Bioorg. Med. Chem. Lett. 2005, 15, 737.
(15) Hu, B.; Ellingboe, J.; Gunawan, L.; Han, S.; Largis, E.; Li,
Z.; Malamas, M.; Mulvey, R.; Oliphant, A.; Sum, F.-W.;
Tillett, J.; Wong, V. Bioorg. Med. Chem. Lett. 2001, 11, 757.
(16) Chaudhuri, K.; Chawla, H. M. Curr. Sci. 1986, 55, 852.
(17) Kauffmann, H.; Kugel, W. Chem. Ber. 1911, 44, 753.
(18) Lin, G.; Zhang, A. Tetrahedron 2000, 56, 7163.
(19) Tang, Z.; Hu, Q. J. Am. Chem. Soc. 2004, 126, 3058.
(20) Zim, D.; Lando, R.; Dupont, J.; Monteiro, A. L. Org. Lett.
2001, 3, 3049.
IR (KBr): 3197, 3093, 2974, 1622, 1534, 1270, 1197, 972, 881
cm–1.
1H NMR (500 MHz, CDCl3): d = 2.48 (s, 3 H), 6.71 (dd, J = 2.5, 9.5
Hz, 1 H), 6.85 (d, J = 2.5 Hz, 1 H), 7.37 (d, J = 7.5 Hz, 2 H), 7.76
(dd, J = 2.0, 6.5 Hz, 2 H), 8.08 (d, J = 9.5 Hz, 1 H), 10.65 (s, 1 H).
13C NMR (125 MHz, CDCl3): d = 21.78, 113.07, 114.57, 126.81,
128.45, 130.15, 131.94, 132.13, 146.31, 155.77, 156.21.
ESI–MS: m/z = 309 [M+ + 1].
Anal. Calcd for C13H11SO6N: C, 50.48; H, 3.58; N, 4.53. Found: C,
50.50; H, 3.64; N, 4.48.
Acknowledgment
(21) Percec, V.; Golding, G. M.; Smidrkal, J.; Weichold, O. J.
Org. Chem. 2004, 69, 3447.
We thank NSFC (20572078) and TJU Young Teacher Foundation
W50501 for financial support.
Synthesis 2006, No. 15, 2478–2482 © Thieme Stuttgart · New York